CN109163960A - A kind of method that microwave-assisted sequence extracts different shape arsenic selenium in flyash - Google Patents
A kind of method that microwave-assisted sequence extracts different shape arsenic selenium in flyash Download PDFInfo
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- CN109163960A CN109163960A CN201811327476.0A CN201811327476A CN109163960A CN 109163960 A CN109163960 A CN 109163960A CN 201811327476 A CN201811327476 A CN 201811327476A CN 109163960 A CN109163960 A CN 109163960A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/44—Sample treatment involving radiation, e.g. heat
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6402—Atomic fluorescence; Laser induced fluorescence
- G01N21/6404—Atomic fluorescence
Abstract
Different extractants is added using microwave dissolver in a kind of method that microwave-assisted sequence extracts different shape arsenic selenium in flyash, and the arsenic selenium of different ADSORPTION STATEs is extracted under different microwave conditions, includes the following steps: the pre-processing of flyash sample；The extraction of non-specific adsorption state (form 1) arsenic selenium；The extraction of specific adsorption state (form 2) arsenic selenium；Unformed and weak crystallization iron aluminum water closes the extraction of oxidizable (form 3) arsenic selenium, and Microwave Extraction power needed for different shape arsenic selenium, temperature and time are different.The method of the present invention substantially reduces extraction time compared to conventional surge extraction scheme, as a result stable, and high duplication and reproducibility is presented.
Description
Technical field
The present invention relates to a kind of methods that microwave-assisted sequence extracts different shape arsenic selenium in flyash, belong to analytical chemistry
Technical field.
Background technique
In worldwide coal consumption, nearly 50% coal consumption is used for power industry, and a large amount of coal burnings cause extremely tight
Trace element (TEs) emission problem of weight.Research has shown that at present, and flying dust has significant enrichment to arsenic and selenium.Solely
With the concentration of arsenic selenium element in flying dust come evaluate its environmental effect be it is inaccurate, the arsenic selenium of different existence state and biology can benefits
With there is substantial connections between property, toxicity and migration etc..The research of major part morphological analysis at present is established in Tessier method
On, follow-up developments go out the BCR method of European Union's certification, but it is not fully up to expectations to the extraction efficiency of arsenic selenium.Wenzel method is directed to
Arsenic selenium element form has carried out extracting optimization in surrounding medium, has been widely used in the analysis of arsenic selenium in various surrounding mediums.
But traditional Wenzel method extracting mode is that concussion is extracted, the period is longer, therefore needs to seek to carry out arsenic Se form in flying dust fast
Speed stablizes the method extracted, this method is still the hot spot and advanced subject of analytical chemistry field research.
Summary of the invention
The present invention is directed to prior art problem, provides a kind of microwave-assisted sequence and extracts different shape arsenic selenium in flyash
Method, the method for the present invention utilizes source of microwave energy heating effect, in conjunction with traditional method for extracting solution, respectively to specific adsorption
State, non-specific adsorption state close oxidizable from amorphous and weak crystallization iron aluminum water and carry out microwave under different microwave conditions
Auxiliary sequence is extracted, and this method greatly shortens the time compared to conventional surge extracting mode, and good repeatability is presented
And reproducibility.
Technical problem of the present invention is solved with following technical solution:
A kind of method that microwave-assisted sequence extracts different shape arsenic selenium in flyash is added different using microwave dissolver
Extractant extracts the arsenic selenium of different ADSORPTION STATEs under different microwave conditions, and described method includes following steps:
A, flying dust sample pre-treatments: after flyash sample is ground after being freeze-dried for 24 hours, 200 meshes are crossed, by sample after sieving
It is stored in 22 ± 1 DEG C, in the drier that relative humidity is 40 ± 5%, is balanced, it is spare；
B, the extraction of non-specific adsorption state (form 1) arsenic selenium: 0.5g the extraction of 1 arsenic of form: is weighed through step a treated powder
12.5mL, 0.05M ammonium sulfate is added in micro-wave diminishing pot in coal ash sample, 3000W, Microwave Extraction 460- at 130 DEG C
Extraction suspension is placed in centrifuge tube and is centrifuged, supernatant liquid filtering is taken to carry out Hydrides AFS spectrum analysis by 500s, residual
Slag B1 continues to employ；The extraction of 1 selenium of form: 0.5g is in addition weighed through step a treated flyash sample in micro-wave diminishing pot, is added
Enter the ammonium sulfate of 12.5mL, 0.05M, 3000W, Microwave Extraction 460-500s at 60 DEG C will extract suspension and be placed in centrifugation
Centrifugation in pipe, takes supernatant liquid filtering to carry out Hydrides AFS spectrum analysis, and residue B2 continues to employ；
C, the extraction of specific adsorption state (form 2) arsenic selenium: non-specific adsorption the extraction of 2 arsenic of form: is extracted to above-mentioned steps b
The total 12.5mL of ammonium dihydrogen phosphate of 0.05M is added in residue B1 after state arsenic in three times, is transferred in counteracting tank, 3000W, 50 DEG C
Extraction suspension is placed in centrifuge tube and is centrifuged, takes supernatant liquid filtering to carry out hydride-atom glimmering by lower Microwave Extraction 220-260s
Light spectrum analysis, residue C1 continue to employ；The extraction of 2 selenium of form: the residue B2 after extracting non-specific adsorption state selenium to above-mentioned steps b
In the total 12.5mL of ammonium dihydrogen phosphate of 0.05M is added in three times, be transferred in counteracting tank, 3000W, Microwave Extraction 220- at 60 DEG C
Extraction suspension is placed in centrifuge tube and is centrifuged, supernatant liquid filtering is taken to carry out Hydrides AFS spectrum analysis by 260s, residual
Slag C2 continues to employ；
D, unformed and weak crystallization iron aluminum water closes the extraction of oxidizable (form 3) arsenic selenium: the extraction of 3 arsenic of form: to residual
The total 12.5mL of ammonium oxalate buffer solution of 0.2M is added in slag C1 in three times, is transferred in counteracting tank, 3000W, microwave at 50 DEG C
110-130s is extracted, extraction suspension is placed in centrifuge tube and is centrifuged, supernatant liquid filtering is taken to carry out Hydrides AFS spectrum
Analysis, residue D1 continue to employ；The extraction of 3 selenium of form: the ammonium oxalate buffer solution that 0.2M is added in three times into residue C2 is total
12.5mL is transferred in counteracting tank, 2000W, Microwave Extraction 110-130s at 50 DEG C, will extract suspension be placed in centrifuge tube from
The heart, takes supernatant liquid filtering to carry out Hydrides AFS spectrum analysis, and residue D2 continues to employ；
E, it the extraction of holocrystalline iron-aluminium oxide reference state (form 4) arsenic selenium: the extraction of 4 arsenic of form: is added into residue D1
Mixed solution 25mL, the 90 DEG C of light-exposed heating water bath 30min of 0.2M ammonium oxalate buffer solution and 0.1M ascorbic acid, centrifugation, take
Supernatant continuously adds 12.5 ml, 0.2M, the ammonium oxalate buffer solution that pH value is 3.25 in residual residue, is protected from light concussion 10
Min, is centrifuged under the same terms and will totally 37.5 ml are uniformly mixed filtering and carry out Hydrides AFS spectrum supernatant twice
Analysis, residue E1 are spare；The extraction of 4 selenium of form: 0.2M ammonium oxalate buffer solution and 0.1M ascorbic acid are added into residue D2
Mixed solution 25mL, 90 DEG C of light-exposed heating water bath 30min, centrifugation, take supernatant；Continuously added in residual residue 12.5 ml,
0.2M, the ammonium oxalate buffer solution that pH value is 3.25 are protected from light 10 min of concussion, are centrifuged and supernatant will be total to twice under the same terms
37.5 ml are uniformly mixed filtering and carry out Hydrides AFS spectrum analysis, and residue E2 is spare；
F, the extraction of residual form (form 5) arsenic selenium: the extraction of 5 arsenic of form: into residue E1 be added 4mL nitric acid, 1mL hydrofluoric acid and
1mL hydrogen peroxide carries out micro-wave digestion, cooling, and centrifugation takes supernatant liquid filtering to carry out Hydrides AFS spectrum analysis；Form 5
The extraction of selenium: 4mL nitric acid, 1mL hydrofluoric acid and 1mL hydrogen peroxide being added into residue E2 and carries out micro-wave digestion, and cooling, centrifugation takes
Supernatant liquid filtering carries out Hydrides AFS spectrum analysis.
The method that above-mentioned microwave-assisted sequence extracts different shape arsenic selenium in flyash, in the step b, 1 arsenic of form
In extraction process, heating extraction is carried out stage by stage, is included the following steps:
First stage sets the pressure of microwave dissolver as 1.0MPa, and power 3000W, temperature rises to 80 DEG C by room temperature, heating
Time is 30s, constant temperature time 30s；
Second stage adjusts the pressure of microwave dissolver as 1.5MPa, and power 3000W, temperature rises to 110 DEG C by 80 DEG C, rises
The warm time is 30s, constant temperature time 30s；
Phase III adjusts the pressure of microwave dissolver as 2.0MPa, and power 3000W, temperature rises to 130 DEG C by 110 DEG C, rises
The warm time is 60s, constant temperature time 480s.
The method that above-mentioned microwave-assisted sequence extracts different shape arsenic selenium in flyash, in the step b, 1 selenium of form
In extraction process, extraction conditions are as follows: set the pressure of microwave dissolver as 1.0MPa, power 3000W, temperature is risen to by room temperature
60 DEG C, heating-up time 30s, constant temperature time 480s.
The method that above-mentioned microwave-assisted sequence extracts different shape arsenic selenium in flyash, in the step c, 2 arsenic of form
In extraction, extraction conditions are as follows: set the pressure of microwave dissolver as 1.0MPa, power 3000W, temperature rises to 50 by room temperature
DEG C, heating-up time 60s, constant temperature time 240s.
The method that above-mentioned microwave-assisted sequence extracts different shape arsenic selenium in flyash, in the step c, 2 selenium of form
In extraction, extraction conditions are as follows: set the pressure of microwave dissolver as 1.0MPa, power 2000W, temperature rises to 60 by room temperature
DEG C, heating-up time 60s, constant temperature time 240s.
The method that above-mentioned microwave-assisted sequence extracts different shape arsenic selenium in flyash, in the step d, 3 arsenic of form
In extraction, extraction conditions are as follows: set the pressure of microwave dissolver as 1.0MPa, power 3000W, temperature rises to 50 by room temperature
DEG C, heating-up time 60s, constant temperature time 120s.
The method that above-mentioned microwave-assisted sequence extracts different shape arsenic selenium in flyash, in the step d, 3 selenium of form
In extraction, extraction conditions are as follows: set the pressure of microwave dissolver as 1.0MPa, power 2000W, temperature rises to 50 by room temperature
DEG C, heating-up time 60s, constant temperature time 120s.
The method that above-mentioned microwave-assisted sequence extracts different shape arsenic selenium in flyash, in the step b-d, the sulfuric acid
Ammonium, ammonium dihydrogen phosphate and ammonium oxalate are guaranteed reagent, the pH value of the ammonium oxalate buffer solution used in the step d for
3.25。
The method that above-mentioned microwave-assisted sequence extracts different shape arsenic selenium in flyash, in the step b-d, the hydrogen of use
The running parameter that compound-Atomic Fluorescence Spectrometer is analyzed are as follows: negative high voltage 270V, lamp current 60mA, atomizer are high
Degree is 8mm, and atomizer temperature is 200 DEG C, carrier gas flux 400mL/min, and shield gas flow amount is 800 mL/min, when reading
Between be 7.0s, delay time 1.3s.
The method that above-mentioned microwave-assisted sequence extracts different shape arsenic selenium in flyash, in the step f, 5 arsenic selenium of form
Resolution extraction, extraction conditions are carried out stage by stage are as follows:
First stage sets the pressure of microwave dissolver as 1.0MPa, and power 3000W, temperature rises to 100 DEG C by room temperature, rises
The warm time is 500s, constant temperature time 60s；
Second stage sets the pressure of microwave dissolver as 1.5MPa, and power 3000W, temperature rises to 130 DEG C by 100 DEG C, rises
The warm time is 200s, constant temperature time 60s；
Phase III sets the pressure of microwave dissolver as 2.0MPa, and power 3000W, temperature rises to 160 DEG C by 130 DEG C, rises
The warm time is 200s, constant temperature time 60s；
Fourth stage sets the pressure of microwave dissolver as 1.0MPa, and power 3000W, temperature rises to 180 DEG C by 160 DEG C, rises
The warm time is 500s, constant temperature time 1200s.
Freeze-drying principle: first the wet feed material in sample is freezed under freezing point, moisture therein is made to be changed into solid-state
Then under vacuum conditions ice is converted into steam and removed by ice, then steamed water with the water vapour coagulator in vacuum system
Vapour condensation, so that sample be made to obtain drying.Freeze-drying can make the moisture in sample directly distil without liquid phase as water
Vapour leaves a void in dry surplus materials when ice distils, thus remains the biological and chemical structural integrity of sample
Property, it is convenient for subsequent chemical analysis.
The principle that source of microwave energy is extracted: polar molecule is quick with the variation of microwave frequency under microwave energy exposure
Transformation orientation, intermolecular mutual frictional impact, absorbing microwave energy causes extracting solution temperature to increase.Microwave heating is a kind of direct
Heating method, not only rapidly, heating is also more evenly, high-efficient compared with traditional heating mode for heating.The variation of microwave frequency
Will lead to the Fast transforms of electromagnetic field orientation, the polar molecule of reagent and sample with quick variation transformation orientation in electromagnetic field, point
Phase mutual friction increases between son, and the surface for being equivalent to reagent and sample is all being constantly updated, and specimen surface constantly contacts new reagent,
The chemical reaction of reagent and sample is promoted to accelerate, to reach the extraction effect of efficient stable.
The present invention replaces the arsenic selenium of different shape in tradition machinery concussion energy source progress flyash using source of microwave energy
Extraction, greatly shorten extraction time, traditional Wenzel method (concussion extracting method) extraction time is more than 24.5h, this hair
Bright method extraction time control improves extraction efficiency within 1h, and extracts with good repeatability and reproducibility；This hair
The arsenic of the bright non-specific adsorption state using Microwave Extraction, the average recovery rate of selenium are respectively the concussion of tradition Wenzel method machinery
The 96.2% of average recovery rate and 114.8%；The average recovery rate of the arsenic selenium of specific adsorption state is respectively tradition Wenzel method
104.5% and 105.4%；It is respectively tradition that unformed and weak crystallization iron aluminum water, which closes oxidizable arsenic selenium average recovery rate,
The 103.9% of Wenzel method and 122.7%, extraction recovery is high, and the time is short, substantially increases extraction efficiency.
Detailed description of the invention
Fig. 1 is extracting method process flow chart of the present invention.
Specific embodiment
The present invention is using carrying out rapidly extracting the characteristics of different shape arsenic selenium in flyash.Arsenic selenium in flyash substantially divides
For three kinds of forms: three kinds of ADSORPTION STATE, reference state and residual form forms.Sequential extraction procedures are a huge sum of moneys under the specific environmental condition of simulation
Belong to the important means of mobility feature.ADSORPTION STATE refers to the mode of occurrence of element being adsorbed in clay, humus and other compositions.
Specific to be divided into non-specific adsorption state and specific adsorption state again, whether the two main distinction is element to certain special groups
Affinity interaction with specificity.ADSORPTION STATE elemental stable is poor, big by such environmental effects, and environmental threat is maximum；Reference state
Refer to the mode of occurrence of element in conjunction with iron aluminum water and oxide, i.e., and iron aluminium hydrous oxide react after the combination that generates
Body or the Partial Elements for being wrapped in sedimentary particle surface.It particularly may be divided into amorphous and weak crystallization iron aluminium hydrous oxide to combine
State and holocrystalline iron aluminum water close oxidizable, and stability is poor under the reducing conditions for the form heavy metal, when the oxygen of environment
When change reduction potential (Eh) changes, this part heavy metal may be released, and have potential risk；Residual form is
Mode of occurrence of element in primary and secondary mineral lattice can exist stably for a long time and the object absorption that is not easy to make a living in nature,
Environmental toxicity is lower.
The invention will be further described with reference to embodiments.
Microwave Extraction experiment is corresponding to carry out blank assay, and blank assay includes that instrument blank and the blank of extraction reagent are real
It tests.Instrument blank assay: after atomic fluorescence device booting operation, instrument blank check is carried out, inspection method is the hydrochloric acid for walking 5%
With mix reducing solution (1% potassium borohydride and 0.5% potassium hydroxide) 5 times, obtain basic blank value, instrument utilizes included work station pair
Test data is calibrated automatically.Sample blank experiment: it is synchronous during sample experiments to carry out the experiment of blank extracting solution, only plus mention
Solution is taken, flyash sample is not added, carries out and sample test is analyzed with the measurement of program.Microwave extract method is respectively to not similar shape
The arsenic selenium of state carries out different durations, the micro-wave digestion auxiliary sequence of different capacity is extracted.
Embodiment 1
Acquire Hebei power plant flyash sample, flyash sample by grinding after through frozen drying for 24 hours after, by from
The dynamic sieving machine of concussion back and forth horizontally crosses 200 meshes, is balanced under the conditions of gained sample is as defined in the GB/T 32722, before experiment
The calibration of pressure and temperature is carried out to microwave dissolver.
The extraction of non-specific adsorption state arsenic: flyash sample 0.5g after weighing Balance Treatment in micro-wave diminishing pot,
12.5mL, 0.05M ammonium sulfate is added, concussion is sufficiently mixed flyash sample with extracting solution, screws counteracting tank inner canister, and
Outer tank is screwed 45 ° in the case where just meeting resistive state, by microwave dissolver program point three steps setting, when the power of microwave dissolver is
When 3000W, temperature are 130 DEG C, micro-wave digestion 8min is carried out, extraction suspension is cooled to room temperature after microwave and is transferred to
In 50mL centrifuge tube, it is centrifuged 15min under 3000r/min revolving speed, takes supernatant through 0.45 μm of micropore water system membrane filtration, by 1mL
Filtered arsenic extracting solution is placed in the dilute hydrochloric acid of 3mL 5% and the thiourea and ascorbic acid mixed solution of 1mL 5%, is sufficiently mixed
Hydrides AFS spectrum analysis is carried out after standing 30min；The extraction step phase of the extraction of non-specific adsorption state selenium and arsenic
Together, one step of microwave dissolver program is set to micro-wave digestion condition, 3000W, micro-wave digestion 8min at 60 DEG C, extract suspension from
The heart is identical as the operating procedure of arsenic, after centrifugal filtration, takes the filtered selenium extracting solution of 1mL to be placed in the dilute hydrochloric acid of 4mL 5%, fills
Hydrides AFS spectrum analysis is carried out after dividing mixing to stand 1h；After atomic fluorescence device booting operation, instrument blank is carried out
It checks, inspection method is hydrochloric acid and mixing reducing solution (1% potassium borohydride and 0.5% potassium hydroxide) 5 times for walking 5%, obtains basic sky
White value, instrument calibrate test data using included work station automatically；Different shape arsenic selenium extraction experiment do 5 groups it is parallel
Experiment, while doing extracting solution blank assay: only plus solution is extracted, flying dust sample, progress and sample test is not added with the inspection of program
Analysis is surveyed, is tested and analyzed after deducting extracting solution blank, available non-specific adsorption state (form 1) arsenic selenium mean concentration difference
For 2.28 ± 0.56 mg/kg, 1.98 ± 0.34 mg/kg.The non-specific adsorption state arsenic selenium that traditional Wenzel method concussion is extracted
Surveyed mean concentration is respectively 2.68 ± 0.62 mg/kg, 1.87 ± 0.42 mg/kg.The method of the present invention Microwave-assisted Extraction is negated
The average recovery rate of specific adsorption state arsenic selenium is respectively 85.1%, 105.9% that tradition concussion is extracted.
The extraction of specific adsorption state arsenic: add in three times into residue B1, B2 after extraction non-specific adsorption state arsenic selenium
The total 12.5mL of ammonium dihydrogen phosphate for entering 0.05M, is transferred back in counteracting tank after residue in centrifuge tube is rinsed well, is uniformly mixed,
The extraction conditions of arsenic selenium are respectively 3000W, 50 DEG C, extract 4min and 2000W, 60 DEG C, extract 4min, the extraction sample after extraction
Processing method and detection method are identical as the method for non-specific adsorption state arsenic selenium.Finally obtain specific adsorption state (form 2)
The mean concentration of arsenic selenium is respectively 6.88 ± 1.14mg/kg, 1.17 ± 0.19 mg/kg, and traditional Wenzel method shakes 2 arsenic of form
The surveyed mean concentration of selenium is respectively 8.56 ± 1.21 mg/kg, 1.11 ± 0.22 mg/kg.Microwave radiation exaraction form 2 of the present invention
Arsenic selenium average recovery rate is 80.4%, the 105.4% of traditional extraction process.
Unformed and weak crystallization iron aluminum water closes the extraction of oxidizable (form 3) arsenic: to extraction specific adsorption state
Arsenic, selenium residue C1, C2 in 0.2M is added in three times respectively, the total 12.5mL of ammonium oxalate buffer solution that pH value is 3.25, will be from
Residue is transferred back in counteracting tank after rinsing well in heart pipe, is uniformly mixed, the extraction conditions of arsenic selenium are respectively 3000W, 50 DEG C, are mentioned
2min and 2000W, 50 DEG C are taken, 2min, extraction sample treatment and detection method and non-specific adsorption after extraction are extracted
The method of state arsenic selenium is identical.The mean concentration for finally obtaining specific adsorption state (form 2) arsenic selenium is respectively 23.82 ± 3.15
Mg/kg, 2.22 ± 0.20 mg/kg, traditional Wenzel method concussion 2 surveyed mean concentration of arsenic selenium of form is respectively 22.93 ± 5.58
Mg/kg, 1.81 ± 0.67 mg/kg.2 arsenic selenium average recovery rate of microwave radiation exaraction form of the present invention is traditional extraction process
103.9%、122.7%。
The extraction of holocrystalline iron-aluminium oxide reference state (form 4) arsenic: oxygen is closed to unformed and weak crystallization iron aluminum water is extracted
0.2 M ammonium oxalate and 0.1 M ascorbic acid mixed solution 25mL are added in residue D1 after compound reference state arsenic, pH value is
3.25, and be uniformly mixed, light-exposed 30 min of water-bath at 90 DEG C.Supernatant is turned after being centrifuged 15min under 3000r/min revolving speed
Move to centrifuge tube；12.5 ml, 0.2M, the ammonium oxalate buffer solution that pH value is 3.25 are continuously added in residual residue, are protected from light concussion
10 min, are centrifuged under the same terms and will totally 37.5 ml are uniformly mixed supernatant twice.Selenium extraction step is identical as arsenic.Detection
The processing of 4 arsenic selenium of form and determination method are identical as above-mentioned form 1 before analyzing, and finally obtain holocrystalline iron-aluminium oxide knot
The mean concentration for closing state (form 4) arsenic selenium is respectively 0.83-0.92mg/kg, 0.14-0.17mg/kg.
The extraction of residual form (form 5) arsenic: 4mL is added into the residue E1 for extracting holocrystalline iron-aluminium oxide reference state arsenic
Nitric acid, 1mL hydrofluoric acid and 1mL hydrogen peroxide mixed solution, are cleared up in microwave dissolver, and heating is carried out after resolution and is caught up with
Acid rushes to 1ml or so, and deionized water is settled to 50 ml, and selenium extraction step is identical as arsenic.The place of 4 arsenic selenium of form before testing and analyzing
Reason and determination method are identical as above-mentioned form 1, and the mean concentration for finally obtaining residual form (form 5) arsenic selenium is respectively
3.42-3.86mg/kg 1.79-1.86mg/kg.
Reproducibility experiment is carried out to extracting method of the present invention, 7 parallel laboratory tests are carried out to sample, relative standard as a result is inclined
Difference shows that microwave extract method of the present invention has good reproducibility between 2.3%-7.7%.
Embodiment 2
The flyash sample of Shanxi power plant is acquired, sample treatment is same as Example 1.
The extraction of non-specific adsorption state arsenic selenium: extracting method and process are same as Example 1, and what is tested and analyzed is non-
Specific adsorption state (form 1) arsenic selenium mean concentration is respectively 3.76 ± 0.43 mg/kg, 2.57 ± 0.33 mg/kg, tradition
The surveyed mean concentration of non-specific adsorption state arsenic selenium that the concussion of Wenzel method is extracted is respectively 3.91 ± 0.62 mg/kg, 2.86 ±
0.42 mg/kg.The average recovery rate of the method for the present invention microwave radiation exaraction non-specific adsorption state arsenic selenium is respectively tradition concussion
96.2%, 89.9% extracted.
The extraction of specific adsorption state arsenic selenium: extracting method and process are same as Example 1, and what is tested and analyzed is special
Property ADSORPTION STATE (form 2) arsenic selenium mean concentration be respectively 5.86 ± 0.72mg/kg, 3.14 ± 0.28 mg/kg, tradition
It is respectively 5.61 ± 0.82 mg/kg, 3.69 ± 0.55 mg/kg that Wenzel method, which shakes 2 the surveyed mean concentration of arsenic selenium of form,.This hair
Bright 2 arsenic selenium average recovery rate of microwave radiation exaraction form is 104.5%, the 85.1% of traditional extraction process.
Unformed and weak crystallization iron aluminum water closes the extraction of oxidizable (form 3) arsenic selenium: extracting method and process with
Embodiment 1 is identical, and the unformed and weak crystallization iron aluminum water tested and analyzed closes being averaged for oxidizable (form 3) arsenic selenium
Concentration is respectively 9.16 ± 0.98 mg/kg, 3.14 ± 0.47 mg/kg, and traditional Wenzel method is shaken to obtain 3 arsenic selenium of form average
Concentration is respectively 10.39 ± 1.84 mg/kg, 2.67 ± 0.41 mg/kg.3 arsenic selenium of microwave radiation exaraction form of the present invention is put down
The equal rate of recovery is 88.2%, the 117.6% of conventional method.
Extracting method and process are same as Example 1, the holocrystalline iron-aluminium oxide reference state (form tested and analyzed
4) mean concentration of arsenic selenium is respectively 1.27-1.39 mg/kg, 0.64-0.77 mg/kg.
Extracting method and process are same as Example 1, the mean concentration of residual form (form 5) the arsenic selenium tested and analyzed
Respectively 5.47-5.91 mg/kg, 2.05-2.54 mg/kg.
Reproducibility experiment is carried out to extracting method of the present invention, 7 parallel laboratory tests are carried out to sample, relative standard as a result is inclined
Difference shows that microwave extract method of the present invention has good reproducibility between 3.1%-8.2%.
Embodiment 3
Acquisition national standard substance GBW08401 is flying dust sample, and sample treatment is same as Example 1.
The extraction of non-specific adsorption state arsenic selenium: extracting method and process are same as Example 1, and what is tested and analyzed is non-
Specific adsorption state (form 1) arsenic selenium mean concentration is respectively 4.04 ± 0.64 mg/kg, 0.31 ± 0.06 mg/kg, tradition
The surveyed mean concentration of non-specific adsorption state arsenic selenium that the concussion of Wenzel method is extracted is respectively 4.55 ± 0.52 mg/kg, 0.27 ±
0.04 mg/kg.The average recovery rate of the method for the present invention microwave radiation exaraction non-specific adsorption state arsenic selenium is respectively tradition concussion
88.8%, 114.8% extracted.
The extraction of specific adsorption state arsenic selenium: extracting method and process are same as Example 1, and what is tested and analyzed is special
Property ADSORPTION STATE (form 2) arsenic selenium mean concentration be respectively 3.56 ± 0.51mg/kg, 0.04 ± 0.02 mg/kg, tradition
It is respectively 4.41 ± 0.65mg/kg, 0.05 ± 0.02 mg/kg that Wenzel method, which shakes 2 the surveyed mean concentration of arsenic selenium of form,.This hair
Bright 2 arsenic selenium average recovery rate of microwave radiation exaraction form is 80.7%, the 80.0% of traditional extraction process.
Unformed and weak crystallization iron aluminum water closes the extraction of oxidizable (form 3) arsenic selenium: extracting method and process with
Embodiment 1 is identical, and the unformed and weak crystallization iron aluminum water tested and analyzed closes being averaged for oxidizable (form 3) arsenic selenium
Concentration is respectively 3.56 ± 0.24 mg/kg, 0.09 ± 0.03mg/kg, and traditional Wenzel method is shaken to obtain 3 arsenic selenium of form average
Concentration is respectively 3.43 ± 0.17 mg/kg, 0.11 ± 0.02 mg/kg.3 arsenic selenium of microwave radiation exaraction form of the present invention is averaged
The rate of recovery is 103.8%, the 81.8% of conventional method.
Extracting method and process are same as Example 1, the holocrystalline iron-aluminium oxide reference state (form tested and analyzed
4) mean concentration of arsenic selenium is below instrument detection limit.
Extracting method and process are same as Example 1, the mean concentration of residual form (form 5) the arsenic selenium tested and analyzed
Respectively 3.66-3.8 mg/kg, 0.59-0.64 mg/kg.
Reproducibility experiment is carried out to extracting method of the present invention, 7 parallel laboratory tests are carried out to sample, relative standard as a result is inclined
Difference shows that microwave extract method of the present invention has good reproducibility between 2.7%-9.4%.
Claims (10)
1. a kind of method that microwave-assisted sequence extracts different shape arsenic selenium in flyash, it is characterised in that: use micro-wave digestion
Different extractants is added in instrument, the arsenic selenium of different ADSORPTION STATEs is extracted under different microwave conditions, described method includes following steps:
A, flying dust sample pre-treatments: after flyash sample is ground after being freeze-dried for 24 hours, 200 meshes are crossed, by sample after sieving
It is stored in 22 ± 1 DEG C, in the drier that relative humidity is 40 ± 5%, is balanced, it is spare；
B, the extraction of non-specific adsorption state (form 1) arsenic selenium: 0.5g the extraction of 1 arsenic of form: is weighed through step a treated powder
12.5mL, 0.05M ammonium sulfate is added in micro-wave diminishing pot in coal ash sample, 3000W, Microwave Extraction 460- at 130 DEG C
Extraction suspension is placed in centrifuge tube and is centrifuged, supernatant liquid filtering is taken to carry out Hydrides AFS spectrum analysis by 500s, residual
Slag B1 continues to employ；The extraction of 1 selenium of form: 0.5g is in addition weighed through step a treated flyash sample in micro-wave diminishing pot, is added
Enter the ammonium sulfate of 12.5mL, 0.05M, 3000W, Microwave Extraction 460-500s at 60 DEG C will extract suspension and be placed in centrifugation
Centrifugation in pipe, takes supernatant liquid filtering to carry out Hydrides AFS spectrum analysis, and residue B2 continues to employ；
C, the extraction of specific adsorption state (form 2) arsenic selenium: non-specific adsorption the extraction of 2 arsenic of form: is extracted to above-mentioned steps b
The total 12.5mL of ammonium dihydrogen phosphate of 0.05M is added in residue B1 after state arsenic in three times, is transferred in counteracting tank, 3000W, 50 DEG C
Extraction suspension is placed in centrifuge tube and is centrifuged, takes supernatant liquid filtering to carry out hydride-atom glimmering by lower Microwave Extraction 220-260s
Light spectrum analysis, residue C1 continue to employ；The extraction of 2 selenium of form: the residue B2 after extracting non-specific adsorption state selenium to above-mentioned steps b
In the total 12.5mL of ammonium dihydrogen phosphate of 0.05M is added in three times, be transferred in counteracting tank, 3000W, Microwave Extraction 220- at 60 DEG C
Extraction suspension is placed in centrifuge tube and is centrifuged, supernatant liquid filtering is taken to carry out Hydrides AFS spectrum analysis by 260s, residual
Slag C2 continues to employ；
D, unformed and weak crystallization iron aluminum water closes the extraction of oxidizable (form 3) arsenic selenium: the extraction of 3 arsenic of form: to residual
The total 12.5mL of ammonium oxalate buffer solution of 0.2M is added in slag C1 in three times, is transferred in counteracting tank, 3000W, microwave at 50 DEG C
110-130s is extracted, extraction suspension is placed in centrifuge tube and is centrifuged, supernatant liquid filtering is taken to carry out Hydrides AFS spectrum
Analysis, residue D1 continue to employ；The extraction of 3 selenium of form: the ammonium oxalate buffer solution that 0.2M is added in three times into residue C2 is total
12.5mL is transferred in counteracting tank, 2000W, Microwave Extraction 110-130s at 50 DEG C, will extract suspension be placed in centrifuge tube from
The heart, takes supernatant liquid filtering to carry out Hydrides AFS spectrum analysis, and residue D2 continues to employ；
E, it the extraction of holocrystalline iron-aluminium oxide reference state (form 4) arsenic selenium: the extraction of 4 arsenic of form: is added into residue D1
Mixed solution 25mL, the 90 DEG C of light-exposed heating water bath 30min of 0.2M ammonium oxalate buffer solution and 0.1M ascorbic acid, centrifugation, take
Supernatant continuously adds 12.5 ml, 0.2M, the ammonium oxalate buffer solution that pH value is 3.25 in residual residue, is protected from light concussion 10
Min, is centrifuged under the same terms and will totally 37.5 ml are uniformly mixed filtering and carry out Hydrides AFS spectrum supernatant twice
Analysis, residue E1 are spare；The extraction of 4 selenium of form: 0.2M ammonium oxalate buffer solution and 0.1M ascorbic acid are added into residue D2
Mixed solution 25mL, 90 DEG C of light-exposed heating water bath 30min, centrifugation, take supernatant；Continuously added in residual residue 12.5 ml,
0.2M, the ammonium oxalate buffer solution that pH value is 3.25 are protected from light 10 min of concussion, are centrifuged and supernatant will be total to twice under the same terms
37.5 ml are uniformly mixed filtering and carry out Hydrides AFS spectrum analysis, and residue E2 is spare；
F, the extraction of residual form (form 5) arsenic selenium: the extraction of 5 arsenic of form: into residue E1 be added 4mL nitric acid, 1mL hydrofluoric acid and
1mL hydrogen peroxide carries out micro-wave digestion, cooling, and centrifugation takes supernatant liquid filtering to carry out Hydrides AFS spectrum analysis；Form 5
The extraction of selenium: 4mL nitric acid, 1mL hydrofluoric acid and 1mL hydrogen peroxide being added into residue E2 and carries out micro-wave digestion, and cooling, centrifugation takes
Supernatant liquid filtering carries out Hydrides AFS spectrum analysis.
2. the method that microwave-assisted sequence according to claim 1 extracts different shape arsenic selenium in flyash, feature exist
In: in the step b, in the extraction process of 1 arsenic of form, heating extraction is carried out stage by stage, is included the following steps:
First stage sets the pressure of microwave dissolver as 1.0MPa, and power 3000W, temperature rises to 80 DEG C by room temperature, heating
Time is 30s, constant temperature time 30s；
Second stage adjusts the pressure of microwave dissolver as 1.5MPa, and power 3000W, temperature rises to 110 DEG C by 80 DEG C, rises
The warm time is 30s, constant temperature time 30s；
Phase III adjusts the pressure of microwave dissolver as 2.0MPa, and power 3000W, temperature rises to 130 DEG C by 110 DEG C, rises
The warm time is 60s, constant temperature time 480s.
3. the method that microwave-assisted sequence according to claim 2 extracts different shape arsenic selenium in flyash, feature exist
In: in the step b, in the extraction process of 1 selenium of form, extraction conditions are as follows: set the pressure of microwave dissolver as 1.0MPa, function
Rate is 3000W, and temperature rises to 60 DEG C, heating-up time 30s, constant temperature time 480s by room temperature.
4. the method that microwave-assisted sequence according to claim 3 extracts different shape arsenic selenium in flyash, feature exist
In: in the step c, in the extraction of 2 arsenic of form, extraction conditions are as follows: set the pressure of microwave dissolver as 1.0MPa, power is
3000W, temperature rise to 50 DEG C, heating-up time 60s, constant temperature time 240s by room temperature.
5. the method that microwave-assisted sequence according to claim 4 extracts different shape arsenic selenium in flyash, feature exist
In: in the step c, in the extraction of 2 selenium of form, extraction conditions are as follows: set the pressure of microwave dissolver as 1.0MPa, power is
2000W, temperature rise to 60 DEG C, heating-up time 60s, constant temperature time 240s by room temperature.
6. the method that microwave-assisted sequence according to claim 5 extracts different shape arsenic selenium in flyash, feature exist
In: in the step d, in the extraction of 3 arsenic of form, extraction conditions are as follows: set the pressure of microwave dissolver as 1.0MPa, power is
3000W, temperature rise to 50 DEG C, heating-up time 60s, constant temperature time 120s by room temperature.
7. the method that microwave-assisted sequence according to claim 6 extracts different shape arsenic selenium in flyash, feature exist
In: in the step d, in the extraction of 3 selenium of form, extraction conditions are as follows: set the pressure of microwave dissolver as 1.0MPa, power is
2000W, temperature rise to 50 DEG C, heating-up time 60s, constant temperature time 120s by room temperature.
8. the method that microwave-assisted sequence according to claim 7 extracts different shape arsenic selenium in flyash, feature exist
In: in the step b-d, the ammonium sulfate, ammonium dihydrogen phosphate and ammonium oxalate are guaranteed reagent, are used in the step d
Ammonium oxalate buffer solution pH value be 3.25.
9. the method that microwave-assisted sequence according to claim 8 extracts different shape arsenic selenium in flyash, feature exist
In: in the step b-d, running parameter that the Hydrides AFS spectrometer of use is analyzed are as follows: negative high voltage is
270V, lamp current 60mA, atomizer height are 8mm, and atomizer temperature is 200 DEG C, carrier gas flux 400mL/min,
Shield gas flow amount is 800 mL/min, reading duration 7.0s, delay time 1.3s.
10. the method that microwave-assisted sequence according to claim 8 extracts different shape arsenic selenium in flyash, feature exist
In: in the step f, 5 arsenic selenium of form carries out resolution extraction, extraction conditions stage by stage are as follows:
First stage sets the pressure of microwave dissolver as 1.0MPa, and power 3000W, temperature rises to 100 DEG C by room temperature, rises
The warm time is 500s, constant temperature time 60s；
Second stage sets the pressure of microwave dissolver as 1.5MPa, and power 3000W, temperature rises to 130 DEG C by 100 DEG C, rises
The warm time is 200s, constant temperature time 60s；
Phase III sets the pressure of microwave dissolver as 2.0MPa, and power 3000W, temperature rises to 160 DEG C by 130 DEG C, rises
The warm time is 200s, constant temperature time 60s；
Fourth stage sets the pressure of microwave dissolver as 1.0MPa, and power 3000W, temperature rises to 180 DEG C by 160 DEG C, rises
The warm time is 500s, constant temperature time 1200s.
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