CN105445208A - Determination method for trace thallium in high-salt waste water - Google Patents
Determination method for trace thallium in high-salt waste water Download PDFInfo
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Abstract
The invention specifically relates to a determination method for trace thallium in high-salt waste water, which belongs to the technical field of heavy metal detection. The determination method for trace thallium in high-salt waste water comprises the following steps: (1) pretreating a waste water sample by using a continuous impurity removal and enrichment method consisting of procedures of extraction, washing, reverse extraction, pH value adjustment of an extraction solution, extraction, washing and reverse extraction; (2) drafting a standard work curve of thallium; (3) detecting the absorbance of the pretreated to-be-detected waste water sample through graphite furnace atomic absorption; and (4) calculating the concentration of the sample according to standard absorbance-concentration relation. According to the invention, extractant used in the method is regenerable and reusable; an added-standard recovery rate reaches 98 to 102%, and a detection limit value is up to 0.1 [mu]g/L, so emission standard detection requirements on thallium in industrial waste water are met; and a blank in determination methods for trace thallium in high-salt waste water is filled in.
Description
Technical field
The invention belongs to heavy metal analysis technical field, be specifically related to the assay method of Determination of Trace Thallium in a kind of high-salt wastewater.
Background technology
Thallium (Tl) is a kind of rare heavy metal element of typical, high degree of dispersion, and geochemistry and crystal chemistry not only have close stone but also has thiophilicity.According to reports, the thallium of the annual production and application in the world is less than 15t, and the nearly 2000 ~ 5000t of thallium produced by industry every year, generation, much larger than demand, does not therefore possess the market condition making product.Reported 56 kinds of thallium minerals in the world at present, and the main association of these mineral is in other ore deposits, especially maximum with sulphide ore.And the iron that we have the call is except iron oxide ore, it is exactly troilite; And the non-ferrous metals such as the copper that in non-ferrous metal, demand is maximum, lead, zinc, antimony, nickel (association is in copper) exist mainly with sulphide ore.China is non-ferrous metal the biggest in the world and gas washing in SA production state and demand state, in nonferrous production process, therefore all can have generation and the discharge of thallium, and cause thallium pollution more and more serious, this has become nationwide problem in China.Thallium is also that one typically poisons element, thallium to the murder by poisoning of biosome with plumbous, mercury is similar, and presents acute toxicity on ecological toxicology.Because itself many places is in trace level, surrounding medium complexity is various in addition, makes the requirement in pre-treatment and detection technique more and more higher.
The assay method of current thallium has a lot, as spectroscopic methodology, atomic absorption method, conventional titration method, electrochemical process and mass spectroscopy and radiochemical analysis etc.Spectrophotometric method is taked the means of organic solvent separation and concentration to measure mostly, is mainly applicable to the analysis of constant and semimicro thallium in water body, but its sensitivity is lower, electrochemical process disturbing factor is many, stable and poor reproducibility, Electrothermo-atomic absorption spectrometry (ETAAS) sensitivity is higher, and sampling is few, easy and simple to handle, but it is more serious by Matrix effects, mass spectroscopy ICP-MS is the plasma mass spectrometry measuring technology of the development eighties in 20th century, this technology provides extremely low detection limit, extremely wide dynamic scope, spectral line is simple, interference is few, analytical precision is high, analysis speed is fast, antijamming capability is strong, highly sensitive, be widely used in the detection of thallium in geology and environment, but when it is for detecting the thallium in high-salt wastewater: there is noise and background drift increase, the matrix effect that the salt that coexists produces can reduce the sensitivity of element to be measured, high salinity waste water ionizes Eroded torch pipe in High temperature ion torch, it is made to be compound in torch tube wall, form white nontransparent thing, quartzy torch pipe is become fragile, easy fracture, reduce the serviceable life of torch pipe, high salinity also easily causes the evaporation of atomizer spout and heat absorption that salinity can be caused to separate out at spout, spray rate is progressively reduced, even block, simultaneously, expensive equipment investment and operating cost make it be difficult to popularize, and the assay method (graphite furnace atomic absorption spectrometry) recommended in GB (GB/T5750.6-2006) adopts direct method or the precipitation method to measure, but it shows as the mensuration of Determination of Trace Thallium in high-salt wastewater, and sample is stablized with poor repeatability, recovery of standard addition is low, preprocessing process is loaded down with trivial details, make the defects such as with medicament classification is many.Therefore, be necessary very much to find a kind of that can solve the problem, detect Determination of Trace Thallium in high sodium salt waste water method.
Summary of the invention
In order to overcome the deficiencies in the prior art and shortcoming, the object of the present invention is to provide the assay method of Determination of Trace Thallium in a kind of high-salt wastewater.
Object of the present invention is achieved through the following technical solutions:
In high-salt wastewater, an assay method for Determination of Trace Thallium, comprises the steps:
(1) sample pretreatment:
1. gather high-salt wastewater water sample, regulate high-salt wastewater water sample pH value to be 3.5 ~ 4.0 with nitric acid or ammoniacal liquor;
2. use the high-salt wastewater water sample after saponification organic phase extracting step (1) adjust ph, obtain organic phase; The organic phase sulfuric acid of 1.5 ~ 5mol/L or nitric acid carry out reextraction 2 ~ 3 times, collect strip liquor; Strip liquor pH value is regulated to be 3.5 ~ 4.0 with ammoniacal liquor;
3. the extraction and back-extraction repeated in step (2) gets process; Collect strip liquor salpeter solution and dilute constant volume, obtain the liquid to be measured that Na ion concentration is less than 30mg/L;
(2) drafting of typical curve: preparation thallium standard serial solution, then adopts the absorbance of sampling Graphite Furnace Atomic Absorption spectrophotometric determination standard serial solution; Take absorbance as ordinate, the concentration of thallium is horizontal ordinate, draw thallium typical curve;
(3) analysis of water sample after pre-service: the absorbance of the liquid to be measured adopting sampling Graphite Furnace Atomic Absorption spectrophotometric determination step (3) obtained;
(4) calculating of thallium mass concentration in wastewater sample: the mass concentration of thallium corresponding under determining this absorbance according to the thallium typical curve in the absorbance measured in step (3) and step (2), then calculates the mass concentration of thallium in water sample;
High-salt wastewater described in step (1) is preferably high sodium salt waste water or high sylvite waste water;
In described high sodium salt waste water, sodium content is preferably 0.5 ~ 40g/L, and the content of thallium is preferably 0.1 ~ 100 μ g/L;
Step (1) if described in high-salt wastewater water sample can not immediate analysis, add nitric acid acidifying, regulate pH to 1 ~ 2, then preserve 4 DEG C below, preservation is no more than 5 days; During mensuration, regulate high-salt wastewater water sample pH to be 3.5 ~ 4.0 with ammoniacal liquor, and then extract; The massfraction of described nitric acid is 65 ~ 98%;
Step (1) 1. described in the massfraction of ammoniacal liquor be preferably 10% ~ 30%;
Step (1) 1. described in the massfraction of nitric acid be 65 ~ 98%;
Step (1) 2. described in saponification organic phase be P204 extractant or P507 extractant and 260# sulfonated kerosene 1:(2.5 ~ 3.5 by volume) mix and form;
The saponification rate of described saponification organic phase is 5 ~ 20%;
Step (1) 2. described in the temperature of extraction be preferably 30 ~ 40 DEG C, the time of extraction is preferably 10 ~ 30min;
Step (1) 2. described in saponification organic phase and volume of water sample than being (0.4 ~ 1): 1;
Step (1) 2. described in organic phase strip before, preferably wash 2 ~ 3 times with water;
Step (1) 2. described in the massfraction of ammoniacal liquor be preferably 10% ~ 30%;
The number of times of the repetition that step (1) is 3. described is preferably 1 time;
Red fuming nitric acid (RFNA) in the salpeter solution that step (1) is 3. described: water (V:V)=1:1, wherein, the massfraction of red fuming nitric acid (RFNA) is 65%;
1000 μ g/L are preferably for the concentration of the thallium standard solution preparing thallium standard serial solution in step (2);
The concentration range of the thallium standard serial solution described in step (2) is 0 ~ 50 μ g/L;
The detection limit of the standard serial solution described in step (2) is preferably 20 μ L;
The related coefficient of the thallium typical curve described in step (2) is greater than 0.995, otherwise repaints;
Imposing a condition of atomic absorption spectrophotometer (AAS) described in step (3) is preferably: described atomic absorption spectrophotometer (AAS) imposes a condition as wavelength 377.6nm, lamp current 3mA, spectral band-width width 0.4nm, graphite furnace heating schedule: baking temperature 110 DEG C, drying time 15s, ashing temperature 500 DEG C, ashing time 15s, atomization temperature 1800 DEG C, atomization time 5s, cleaning temp 2600 DEG C, cleaning time 2s, matrix modifier: 5 μ L massfractions are the palladium nitrate solution of 0.3%;
The detection limit of the liquid to be measured described in step (3) is preferably 20 μ L;
Step (3) if described in liquid to be measured in liquid to be checked the concentration of thallium to be above standard curve ranges, then available salpeter solution is surveyed by multiple dilutions again, is multiplied by extension rate during calculating; Red fuming nitric acid (RFNA) in described salpeter solution: water (V:V)=1:1, wherein, the massfraction of red fuming nitric acid (RFNA) is 65%;
In calculating water sample described in step (4), the formula of the mass concentration of thallium is:
In formula:
P
1for the mass concentration (μ g/L) of thallium in water sample;
P
2for checking in the mass concentration (μ g/L) of thallium in water sample from thallium typical curve;
The volume (mL) that V is institute's water sampling;
V
1for water sample concentrate after volume (mL);
The present invention has following advantage and effect relative to prior art:
Compared with Determination of Trace Thallium detection technique in existing waste water, this detection method compensate in high-salt wastewater the blank detecting Determination of Trace Thallium, this method can eliminate the interference of sodion in high-salt wastewater, potassium ion and chlorion, extractant used can regenerate to be reused, recovery of standard addition reaches 98 ~ 102%, detect limit value can reach 0.1 μ g/L, detect and operating cost low, meet the emission standard testing requirement of thallium in industrial waste water, detect significant to the control of thallium in enterprise's high-salt wastewater and process.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
A detection method for Determination of Trace Thallium in high-salt wastewater, comprises the following steps:
(1) waste water collection, transfer and preservation: get hydrometallurgy industry factory waste water water sample 200mL (sodium content is 40g/L, and thallium content is 8.10 μ g/L), sealing, analyzes; If can not immediate analysis, add nitric acid acidifying, regulate pH to 1, then preserve 4 DEG C below, preservation is no more than 5 days; During mensuration, regulate high-salt wastewater water sample pH to be 3.82 with ammoniacal liquor, and then extract; The massfraction of described nitric acid is 65%;
(2) sample pretreatment:
1. be transferred to from sampling jar by water sample in 500mL beaker, each pure water 10mL that uses rinses polyethylene bottle 2 times simultaneously, and the water after flushing is poured in transfer water sample successively, mixing; Be 3.82 with the ammoniacal liquor water transfer sample pH that massfraction is 15%;
2. with saponification rate be 15% saponification organic phase (by P204 extractant and 260# sulfonated kerosene by volume 1:3 form) 100mL extracts water sample, stirring reaction time 20min at 35 DEG C; Standing clarification separates organic phase, and aqueous phase is not; By organic phase that pure water separates 2 times, washings are not; After washing, the sulfuric acid of organic 2mol/L carries out back extraction 2 times, collects 2 strip liquors, mixing; Strip liquor pH value is adjusted to be 3.95 with the ammoniacal liquor that massfraction is 30%;
3. with new, saponification rate be 15% saponification organic phase (by P204 extractant and 260# sulfonated kerosene by volume 1:3 form) and step 2. adjust the strip liquor after pH repeat step 2. in extraction-2 time wash-2 stripping process; Collect last 2 strip liquors in 100mL volumetric flask; With (1+99) salpeter solution (red fuming nitric acid (RFNA): water (V:V)=1:1, wherein, the massfraction of red fuming nitric acid (RFNA) is 65%) dilution be settled to scale, shake up, obtain liquid to be measured, pipetting the mass concentration that 20mL liquid atomic absorption spectrophotometry to be measured surveys wherein sodium is 11.02mg/L, and remaining 80mL sampling Graphite Furnace Atomic Absorption spectrophotometer carries out detection thallium;
(3) drafting of typical curve: pipette 0.00 respectively, 0.50,1.00,2.00,3.00,4.00,5.00mL thallium standard solution (1000 μ g/L) is in 100mL polyethylene volume bottle, be settled to scale with nitric acid (1+99) solution, shake up; Standard series concentration is respectively 0.0,5.0,10.0,20.0,30.0,40.0,50.0 μ g/L, adds 20 μ L successively according to reference instrument condition by low concentration to high concentration in graphite-pipe, measures absorbance; Take absorbance as ordinate, the concentration of thallium (μ g/L) is horizontal ordinate, draw thallium typical curve; The related coefficient of typical curve is greater than 0.995, otherwise repaints;
(4) analysis of water sample after pre-service: sampling Graphite Furnace Atomic Absorption spectrophotometer is adjusted to optimum Working, pipette 20 μ L samples to detect, described atomic absorption spectrophotometer (AAS) imposes a condition as wavelength 377.6nm, lamp current 3mA, spectral band-width width 0.4nm, graphite furnace heating schedule: baking temperature 110 DEG C, drying time 15s; Ashing temperature 500 DEG C, ashing time 15s; Atomization temperature 1800 DEG C, atomization time 5s, cleaning temp 2600 DEG C, cleaning time 2s, matrix modifier: 5 μ L massfractions are the palladium nitrate solution of 0.3%; If the concentration of thallium is above standard curve ranges in measuring samples, then available (1+99) salpeter solution is surveyed by multiple dilutions again, is multiplied by extension rate during calculating, does sample blank experiment simultaneously;
(5) calculating of thallium mass concentration in wastewater sample: adopt typical curve standard measure, the mass concentration of the thallium that the absorbance measured according to water sample after pre-service is corresponding find out this absorbance on thallium typical curve under, then be calculated as follows the mass concentration of thallium in water sample:
In formula:
P
1the mass concentration of thallium in-water sample, μ g/L;
P
2-from thallium typical curve, check in the mass concentration of thallium in water sample, μ g/L;
The volume of V-institute's water sampling, mL;
V
1volume after-water sample concentrates, mL;
Obtain four parallel target water samples to be measured with same processing mode, carry out analyzing and calculate the content of thallium, obtaining analysis result: be followed successively by 8.25 μ g/L, 8.06 μ g/L, 8.12 μ g/L, 8.28 μ g/L, average recovery rate is 100.01%.
Embodiment 2
A detection method for Determination of Trace Thallium in high-salt wastewater, comprises the following steps:
(1) waste water collection, transfer and preservation: get hydrometallurgy industry factory plant of water disposal efflux wastewater water sample 400mL (sodium content is 5g/L, and thallium content is 0.52 μ g/L), sealing, analyzes; Described efflux wastewater is raffinate waste water through removing heavy metals precipitation, waste water after sand filtration tone pitch; If can not immediate analysis, add nitric acid acidifying, regulate pH to 2, then preserve 4 DEG C below, preservation is no more than 5 days; During mensuration, regulate high-salt wastewater water sample pH to be 3.95 with ammoniacal liquor, and then extract; The massfraction of described nitric acid is 98%;
(2) sample pretreatment:
1. be transferred to from sampling jar by water sample in 1000mL beaker, each pure water 10mL that uses rinses polyethylene bottle 3 times simultaneously, and the water after flushing is poured in transfer water sample successively, mixing; Be 3.95 with the ammoniacal liquor water transfer sample pH that massfraction is 30%;
2. with saponification rate be 15.21% saponification organic phase (by P507 extractant and 260# sulfonated kerosene by volume 1:2.5 form) 200mL extracts water sample, stirring reaction time 30min at 38 DEG C; Standing clarification separates organic phase, and aqueous phase is not; By organic phase that pure water separates 2 times, washings are not; After washing, the sulfuric acid of organic 1.8mol/L carries out back extraction 2 times, collects 2 strip liquors, mixing; Strip liquor pH value is adjusted to be 3.92 with the ammoniacal liquor that massfraction is 30%;
3. with new, saponification rate be 15.21% saponification organic phase (by P507 extractant and 260# sulfonated kerosene by volume 1:2.5 form) and step 2. adjust the strip liquor after pH repeat step 2. in extraction-2 time wash-2 stripping process; Collect last 2 strip liquors in 100mL volumetric flask; With (1+99) salpeter solution (red fuming nitric acid (RFNA): water (V:V)=1:1, wherein, the massfraction of red fuming nitric acid (RFNA) is 65%) dilution be settled to scale, shake up, obtain liquid to be measured, pipetting the mass concentration that 20mL liquid atomic absorption spectrophotometry to be measured surveys wherein sodium is 8.32mg/L, and remaining 80mL sampling Graphite Furnace Atomic Absorption spectrophotometer carries out detection thallium;
(3) drafting of typical curve: pipette 0.00 respectively, 0.50,1.00,2.00,3.00,4.00,5.00mL thallium standard solution (1000 μ g/L) is in 100mL polyethylene volume bottle, be settled to scale with nitric acid (1+99) solution, shake up; Standard series concentration is respectively 0.0,5.0,10.0,20.0,30.0,40.0,50.0 μ g/L, adds 20 μ L successively according to reference instrument condition by low concentration to high concentration in graphite-pipe, measures absorbance; Take absorbance as ordinate, the concentration of thallium (μ g/L) is horizontal ordinate, draw thallium typical curve; The related coefficient of typical curve is greater than 0.995, otherwise repaints;
(4) analysis of water sample after pre-service: sampling Graphite Furnace Atomic Absorption spectrophotometer is adjusted to optimum Working, pipette 20 μ L samples to detect, described atomic absorption spectrophotometer (AAS) imposes a condition as wavelength 377.6nm, lamp current 3mA, spectral band-width width 0.4nm, graphite furnace heating schedule: baking temperature 110 DEG C, drying time 15s; Ashing temperature 500 DEG C, ashing time 15s; Atomization temperature 1800 DEG C, atomization time 5s, cleaning temp 2600 DEG C, cleaning time 2s, matrix modifier: 5 μ L massfractions are the palladium nitrate solution of 0.3%; If the concentration of thallium is above standard curve ranges in measuring samples, then available (1+99) salpeter solution is surveyed by multiple dilutions again, is multiplied by extension rate during calculating, does sample blank experiment simultaneously;
(5) calculating of thallium mass concentration in wastewater sample: adopt typical curve standard measure, the mass concentration of the thallium that the absorbance measured according to water sample after pre-service is corresponding find out this absorbance on thallium typical curve under, then be calculated as follows the mass concentration of thallium in water sample:
In formula:
P
1the mass concentration of thallium in-water sample, μ g/L;
P
2-from thallium typical curve, check in the mass concentration of thallium in water sample, μ g/L;
The volume of V-institute's water sampling, mL;
V
1volume after-water sample concentrates, mL.
Obtain four parallel target water samples to be measured with same processing mode, carry out analyzing and calculate the content of thallium, obtaining analysis result: be followed successively by 0.513 μ g/L, 0.530 μ g/L, 0.505 μ g/L, 0.522 μ g/L, average recovery rate is 99.5%.
Embodiment 3
A detection method for Determination of Trace Thallium in high-salt wastewater, comprises the following steps:
(1) waste water collection, transfer and preservation: get hydrometallurgy industry factory waste water water sample 300mL (sodium content is 0.5g/L, and thallium content is 0.1 μ g/L), sealing, analyzes; If can not immediate analysis, add nitric acid acidifying, regulate pH to 1.5, then preserve 4 DEG C below, preservation is no more than 5 days; During mensuration, regulate high-salt wastewater water sample pH to be 3.5 with ammoniacal liquor, and then extract; The massfraction of described nitric acid is 80%;
(2) sample pretreatment part:
1. be transferred to from sampling jar by water sample in 500mL beaker, each pure water 10mL that uses rinses polyethylene bottle 2 times simultaneously, and the water after flushing is poured in transfer water sample successively, mixing; Be 3.5 with the ammoniacal liquor water transfer sample pH that massfraction is 20%;
2. with saponification rate be 5% saponification organic phase (by P204 extractant and 260# sulfonated kerosene by volume 1:3.5 form) 100mL extracts water sample, stirring reaction time 10min at 40 DEG C; Standing clarification separates organic phase, and aqueous phase is not; By organic phase that pure water separates 3 times, washings are not; After washing, the nitric acid of organic 5mol/L carries out back extraction 3 times, collects 3 strip liquors, mixing; Strip liquor pH value is adjusted to be 3.5 with the ammoniacal liquor that massfraction is 20%;
3. with new, saponification rate be 5% saponification organic phase (by P204 extractant and 260# sulfonated kerosene by volume 1:3.5 form) and step 2. adjust the strip liquor after pH repeat step 2. in extraction-3 time wash-3 stripping process; Collect last 3 strip liquors in 100mL volumetric flask; With (1+99) salpeter solution (red fuming nitric acid (RFNA): water (V:V)=1:1, wherein, the massfraction of red fuming nitric acid (RFNA) is 65%) dilution be settled to scale, shake up, obtain liquid to be measured, pipetting the mass concentration that 20mL liquid atomic absorption spectrophotometry to be measured surveys wherein sodium is 5mg/L, and remaining 80mL sampling Graphite Furnace Atomic Absorption spectrophotometer carries out detection thallium;
(3) drafting of typical curve: pipette 0.00 respectively, 0.50,1.00,2.00,3.00,4.00,5.00mL thallium standard solution (1000 μ g/L) is in 100mL polyethylene volume bottle, be settled to scale with nitric acid (1+99) solution, shake up; Standard series concentration is respectively 0.0,5.0,10.0,20.0,30.0,40.0,50.0 μ g/L, adds 20 μ L successively according to reference instrument condition by low concentration to high concentration in graphite-pipe, measures absorbance; Take absorbance as ordinate, the concentration of thallium (μ g/L) is horizontal ordinate, draw thallium typical curve; The related coefficient of typical curve is greater than 0.995, otherwise repaints;
(4) analysis of water sample after pre-service: sampling Graphite Furnace Atomic Absorption spectrophotometer is adjusted to optimum Working, pipette 20 μ L samples to detect, described atomic absorption spectrophotometer (AAS) imposes a condition as wavelength 377.6nm, lamp current 3mA, spectral band-width width 0.4nm, graphite furnace heating schedule: baking temperature 110 DEG C, drying time 15s; Ashing temperature 500 DEG C, ashing time 15s; Atomization temperature 1800 DEG C, atomization time 5s, cleaning temp 2600 DEG C, cleaning time 2s, matrix modifier: 5 μ L massfractions are the palladium nitrate solution of 0.3%; If the concentration of thallium is above standard curve ranges in measuring samples, then available (1+99) salpeter solution is surveyed by multiple dilutions again, is multiplied by extension rate during calculating, does sample blank experiment simultaneously;
(5) calculating of thallium mass concentration in wastewater sample: adopt typical curve standard measure, the mass concentration of the thallium that the absorbance measured according to water sample after pre-service is corresponding find out this absorbance on thallium typical curve under, then be calculated as follows the mass concentration of thallium in water sample:
In formula:
P
1the mass concentration of thallium in-water sample, μ g/L;
P
2-from thallium typical curve, check in the mass concentration of thallium in water sample, μ g/L;
The volume of V-institute's water sampling, mL;
V
1volume after-water sample concentrates, mL;
Obtain four parallel target water samples to be measured with same processing mode, carry out analyzing and calculate the content of thallium, obtaining analysis result: be followed successively by 0.092 μ g/L, 0.099 μ g/L, 0.112 μ g/L, 0.104 μ g/L, average recovery rate is 101.75%.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from Spirit Essence of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. the assay method of Determination of Trace Thallium in high-salt wastewater, is characterized in that comprising the steps:
(1) sample pretreatment:
1. gather high-salt wastewater water sample, regulate high-salt wastewater water sample pH value to be 3.5 ~ 4.0 with nitric acid or ammoniacal liquor;
2. use the high-salt wastewater water sample after saponification organic phase extracting step (1) adjust ph, obtain organic phase; The organic phase sulfuric acid of 1.5 ~ 5mol/L or nitric acid carry out reextraction 2 ~ 3 times, collect strip liquor; Strip liquor pH value is regulated to be 3.5 ~ 4.0 with ammoniacal liquor;
3. the extraction and back-extraction repeated in step (2) gets process; Collect strip liquor salpeter solution and dilute constant volume, obtain the liquid to be measured that Na ion concentration is less than 30mg/L;
(2) drafting of typical curve: preparation thallium standard serial solution, then adopts the absorbance of sampling Graphite Furnace Atomic Absorption spectrophotometric determination standard serial solution; Take absorbance as ordinate, the concentration of thallium is horizontal ordinate, draw thallium typical curve;
(3) analysis of water sample after pre-service: the absorbance of the liquid to be measured adopting sampling Graphite Furnace Atomic Absorption spectrophotometric determination step (3) obtained;
(4) calculating of thallium mass concentration in wastewater sample: the mass concentration of thallium corresponding under determining this absorbance according to the thallium typical curve in the absorbance measured in step (3) and step (2), then calculates the mass concentration of thallium in water sample.
2., according to the assay method of Determination of Trace Thallium in the high-salt wastewater described in claim 1, it is characterized in that:
High-salt wastewater described in step (1) is high sodium salt waste water or high sylvite waste water.
3., according to the assay method of Determination of Trace Thallium in the high-salt wastewater described in claim 1, it is characterized in that:
Step (1) 2. described in saponification organic phase be P204 extractant or P507 extractant and 260# sulfonated kerosene 1:(2.5 ~ 3.5 by volume) mix and form.
4., according to the assay method of Determination of Trace Thallium in the high-salt wastewater described in claim 1, it is characterized in that:
The saponification rate of described saponification organic phase is 5 ~ 20%.
5., according to the assay method of Determination of Trace Thallium in the high-salt wastewater described in claim 1, it is characterized in that:
Step (1) 2. described in saponification organic phase and volume of water sample than being (0.4 ~ 1): 1.
6., according to the assay method of Determination of Trace Thallium in the high-salt wastewater described in claim 1, it is characterized in that:
Step (1) 2. described in the temperature of extraction be 30 ~ 40 DEG C, the time of extraction is 10 ~ 30min.
7., according to the assay method of Determination of Trace Thallium in the high-salt wastewater described in claim 1, it is characterized in that:
Volume ratio=the 1:1 of red fuming nitric acid (RFNA) and water in the salpeter solution that step (1) is 3. described, wherein, the massfraction of red fuming nitric acid (RFNA) is 65%.
8., according to the assay method of Determination of Trace Thallium in the high-salt wastewater described in claim 1, it is characterized in that:
The concentration range of the thallium standard serial solution described in step (2) is 0 ~ 50 μ g/L.
9., according to the assay method of Determination of Trace Thallium in the high-salt wastewater described in claim 1, it is characterized in that:
Atomic absorption spectrophotometer (AAS) described in step (3) impose a condition as: described atomic absorption spectrophotometer (AAS) imposes a condition as wavelength 377.6nm, lamp current 3mA, spectral band-width width 0.4nm, graphite furnace heating schedule: baking temperature 110 DEG C, drying time 15s, ashing temperature 500 DEG C, ashing time 15s, atomization temperature 1800 DEG C, atomization time 5s, cleaning temp 2600 DEG C, cleaning time 2s, matrix modifier: 5 μ L massfractions are the palladium nitrate solution of 0.3%.
10., according to the assay method of Determination of Trace Thallium in the high-salt wastewater described in claim 1, it is characterized in that:
In calculating water sample described in step (4), the formula of the mass concentration of thallium is:
In formula:
P
1for the mass concentration of thallium in water sample;
P
2for checking in the mass concentration of thallium in water sample from thallium typical curve;
V is the volume of institute's water sampling;
V
1for water sample concentrate after volume.
Priority Applications (1)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106053462A (en) * | 2016-05-25 | 2016-10-26 | 中华人民共和国防城港出入境检验检疫局 | Method for measuring trace thallium in water |
| CN106323948A (en) * | 2016-10-25 | 2017-01-11 | 福建紫金矿冶测试技术有限公司 | Method for measuring content of thallium in ore and ore concentrate |
| CN106970234A (en) * | 2016-05-09 | 2017-07-21 | 姚衡 | The chemical analysis method of heavy metal ion content in a kind of water |
| CN111175270A (en) * | 2020-02-11 | 2020-05-19 | 道道全粮油股份有限公司 | Method for detecting trace arsenic in vegetable oil by extraction and dry ashing atomic fluorescence |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6064474A (en) * | 1998-02-06 | 2000-05-16 | Optical Sensors, Inc. | Optical measurement of blood hematocrit incorporating a self-calibration algorithm |
| US20020050567A1 (en) * | 2000-05-30 | 2002-05-02 | Thierry Boudet | Method and apparatus for detecting gases |
| US20040002162A1 (en) * | 2002-06-27 | 2004-01-01 | Leugers Mary Anne | Transmission infrared spectroscopy array and method |
| US20040233448A1 (en) * | 2001-09-28 | 2004-11-25 | Yves Goulas | Device for measuring light absorption characteristics of a biological tissue sample |
| CN102768191A (en) * | 2012-07-31 | 2012-11-07 | 浙江中一检测研究院股份有限公司 | Method for easily detecting trace thallium in water |
-
2015
- 2015-12-10 CN CN201510920283.6A patent/CN105445208B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6064474A (en) * | 1998-02-06 | 2000-05-16 | Optical Sensors, Inc. | Optical measurement of blood hematocrit incorporating a self-calibration algorithm |
| US20020050567A1 (en) * | 2000-05-30 | 2002-05-02 | Thierry Boudet | Method and apparatus for detecting gases |
| US20040233448A1 (en) * | 2001-09-28 | 2004-11-25 | Yves Goulas | Device for measuring light absorption characteristics of a biological tissue sample |
| US20040002162A1 (en) * | 2002-06-27 | 2004-01-01 | Leugers Mary Anne | Transmission infrared spectroscopy array and method |
| CN102768191A (en) * | 2012-07-31 | 2012-11-07 | 浙江中一检测研究院股份有限公司 | Method for easily detecting trace thallium in water |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106970234A (en) * | 2016-05-09 | 2017-07-21 | 姚衡 | The chemical analysis method of heavy metal ion content in a kind of water |
| CN106053462A (en) * | 2016-05-25 | 2016-10-26 | 中华人民共和国防城港出入境检验检疫局 | Method for measuring trace thallium in water |
| CN106323948A (en) * | 2016-10-25 | 2017-01-11 | 福建紫金矿冶测试技术有限公司 | Method for measuring content of thallium in ore and ore concentrate |
| CN106323948B (en) * | 2016-10-25 | 2019-01-08 | 福建紫金矿冶测试技术有限公司 | The measuring method of thallium amount in a kind of ore and concentrate |
| CN111175270A (en) * | 2020-02-11 | 2020-05-19 | 道道全粮油股份有限公司 | Method for detecting trace arsenic in vegetable oil by extraction and dry ashing atomic fluorescence |
| CN111175270B (en) * | 2020-02-11 | 2022-03-11 | 道道全粮油股份有限公司 | Method for detecting trace arsenic in vegetable oil by extraction and dry ashing atomic fluorescence |
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