CN104502467A - Determination method of arsenic valence - Google Patents
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- CN104502467A CN104502467A CN201410665262.XA CN201410665262A CN104502467A CN 104502467 A CN104502467 A CN 104502467A CN 201410665262 A CN201410665262 A CN 201410665262A CN 104502467 A CN104502467 A CN 104502467A
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Abstract
The invention discloses a determination method of arsenic valence. The method comprises the steps of: (1) adding an extracting solution which is a mixed solution of H3PO4 and ascorbic acid into a sample to be measured, which is coal or household garbage incineration ash, soil or sludge, completely releasing the produced gas, digesting by microwave, filtering a digestion liquid, washing the residue by an extracting solution, collecting the washing liquid, mixing the extracting solution with the filtrate, and making up to volume; (2) separating trivalent and pentavalent arsenic; (3) reducing the separated trivalent and pentavalent arsenic to obtain arsenic hydride gas; and (4) determining the arsenic hydride gas obtained by reduction of arsenic in different valence, so as to obtain the content of trivalent and pentavalent arsenic in the sample to be measured. The method can achieve nondestructive extraction and fast and effective separation of trivalent and pentavalent arsenic, has the advantages of high accuracy of the determination results, simple operation, low cost on determination and equipment maintenance, and is applicable to analysis and determination of arsenic form in solid wastes such as fuel burning ash, soil and sludge.
Description
Technical field
The invention belongs to arsenium morphological analysis technical field in fuel combustion products, more specifically, relate to a kind of assay method of arsenic valence state.
Background technology
The burning of the fuel such as coal, living beings and municipal solid wastes is with the generation of a large amount of incineration residue.The toxic trace elements arsenic deposited is composed normal with gaseous state trivalent arsenic As under high-temp combustion in fuel
2o
3form be discharged in flue gas, in fuel under the compound effects such as calcium, iron, aluminium, As
2o
3oxidation is generated the less pentavalent arsenic hydrochlorate of volatility, be cured in flying dust or bottom ash, reduce to the discharge in air; Meanwhile part As
2o
3can be trapped by flying dust by physisorption at low temperatures.Thus, arsenic mainly exists with the inorganic arsenic form of trivalent and pentavalent in fuel incineration residue.In the process disposal process of lime-ash, in lime-ash, part arsenic will leach in soil and water body, cause great destruction to the ecologic environment of surrounding.Arsenic, to the harm of human body, is not only decided by the total amount of arsenic, also depends on the valence state of arsenic, and arsenious toxicity will far above pentavalent arsenic.The valence state of arsenic in fuel combustion lime-ash is measured, not only can predict the latency environment harm caused by arsenic in grey Slag treatment disposal process, and the Transport And Transformation mechanism of arsenic in combustion process can be resolved, there is provided important reference frame for realizing the release control of arsenic in fuel combustion process, thus there is important researching value and realistic meaning.
At present, the determination object of the arsenic valence state mainly sample such as water body, medicine, tobacco.Such as, publication number is that the arsenic of different valence state in seawater is reduced by different reductive agent by the Chinese patent application of CN102262078A respectively, utilizes hydride generation system to carry out separation determination in conjunction with atomic fluorescence spectrophotometry to trivalent arsenic in seawater and pentavalent arsenic.Publication number is that the Chinese patent application of CN102692470A adopts bionical solvent to extract the arsenic of different valence state in medicine realgar under magnetic agitation and ultrasonication, carries out quantitative test by High performance liquid chromatography-inductively coupled plasma mass spectrometry coupling technique to the arsenic of different valence state in extract.Publication number is that the Chinese patent application of CN103033571A discloses an assay method growing tobacco middle different valence state arsenic, utilize methanol/water for the arsenic of different valence state in extraction agent ultrasonic extraction tobacco, and then adopt High performance liquid chromatography-inductively coupled plasma mass spectrometry coupling technique to measure the arsenic of different valence state in extract.
But, compared to water and organic sample, arsenic in fuel incineration residue mainly exists with inorganic trivalent arsenic and pentavalent arsenic, due to physical-chemical reaction complicated under high temperature, the occurrence patterns of arsenic is very complicated, be difficult to carry out harmless extraction, be embodied in: the combining form of (1) arsenic in fuel incineration residue is comparatively more stable in organic sample, thus adopts water, methyl alcohol or bionical solvent to be difficult to realize the high efficiency extraction to arsenic in lime-ash; (2) some high oxides will be generated in fuel combustion process, in the leaching process of arsenic, very easily trivalent arsenic will be oxidized to pentavalent arsenic, thus cause measurement result distortion; (3) there is the leachability material of large amount of complex in incineration residue, will the separating effect of different valence state arsenic be affected.
Summary of the invention
For above defect or the Improvement requirement of prior art, the invention provides a kind of assay method of arsenic valence state, the harmless extraction that can realize trivalent arsenic and pentavalent arsenic be effectively separated fast, measurement result accuracy is high, and it is simple to operate, measure and cost of equipment maintenance low, be applicable to arsenic morphology in the solid waste such as fuel incineration residue, soil or mud analysis measure.
For achieving the above object, the invention provides a kind of assay method of arsenic valence state, it is characterized in that, comprise the steps: that (1) adds extract by solid-to-liquid ratio 1:100 ~ 150g/mL to containing in arsenic testing sample, after air release to be generated is complete, cleared up by microwave, digestion solution is filtered, wash residue with extract, collect cleansing solution, it is settled to predetermined with filtrate mixing; Wherein, extract is H
3pO
4with the mixed solution of ascorbic acid, H in extract
3pO
4concentration be 0.1 ~ 1.0mol/L, the concentration of ascorbic acid is 0.2 ~ 0.5mol/L; (2) trivalent arsenic in mixed liquor step (1) obtained with high performance liquid chromatograph is separated with pentavalent arsenic; (3) utilize hydride generator successively to reduce to isolated trivalent arsenic and pentavalent arsenic, obtain arsine gas; (4) utilize atomic fluorescence spectrometer to reduce to the arsenic of different valence state the arsine gas obtained to measure, obtain the concentration of trivalent arsenic and pentavalent arsenic in the mixed liquor that step (1) obtains, thus obtain the content of trivalent arsenic and pentavalent arsenic in testing sample.
Preferably, in described step (2), mobile phase is pH value is the potassium dihydrogen phosphate of 6.5 ~ 6.8 and the mixed solution of sodium hydrogen phosphate, and flow velocity is 1.0 ~ 1.5mL/min, and chromatographic column selects anion chromatographic column.
Preferably, in described step (3), the reagent that hydride occurs to use is the first reagent and the second reagent, and wherein, the first reagent is HCl, and the second reagent is the KBH containing KOH
4solution.
Preferably, described is coal incineration residue, domestic refuse incineration ash, soil or mud containing arsenic testing sample.
In general, the above technical scheme conceived by the present invention compared with prior art, has following beneficial effect:
1, the combination stability in view of arsenic in fuel incineration residue is better, selects certain density H
3pO
4as extraction agent, in the periodic table of elements, phosphorus and arsenic are in identity element race, corresponding phosphate radical and the character of arsenate and arsenous anion comparatively close, in the leaching process of solution, phosphate radical is easier displaces arsenate or arsenous anion from the arsenical of lime-ash, and promote arsenic by microwave action rapid extraction is out from lime-ash simultaneously.
2, in order to prevent the oxidizing substance existed in lime-ash to be oxidized trivalent arsenic, in extraction agent, add the appropriate ascorbic acid with certain inoxidizability, thus realize the harmless extraction of trivalent arsenic and pentavalent arsenic in lime-ash.
3, select phosphate buffered solution as mobile phase, can the arsenic of the fast and effeciently different valence state of separation and Extraction, avoid the impact of other ion pair arsenic separation determination simultaneously.
4, by the content of hydride generation-atomic fluorescence spectrometric instrument quantitative test different valence state arsenic, wherein high performance liquid chromatography-atomic fluorescence spectrophotometry coupling technique, compared to simple to operate high performance liquid chromatography-Inductively coupled plasma mass spectrometry coupling technique, and measure and cost of equipment maintenance lower.
5, the measurement result accuracy of the assay method of arsenic valence state of the present invention is high, can be used for the valence distribution specificity analysis that different qualities fuel burns arsenic in the lime-ash produced, the analysis that also may be used for arsenic morphology in the solid waste such as the soil of class ash & slag dam, mud measures.
Accompanying drawing explanation
Fig. 1 is the assay method process flow diagram of the arsenic valence state of the embodiment of the present invention;
Fig. 2 be the arsenate of analysis five kinds of variable concentrations obtain with the mixed standard solution of arsenous anion be separated spectral line.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.In addition, if below in described each embodiment of the present invention involved technical characteristic do not form conflict each other and just can mutually combine.
As shown in Figure 1, the assay method of the arsenic valence state of the embodiment of the present invention comprises the steps:
(1) in testing sample, add extract by solid-to-liquid ratio 1:100 ~ 150g/mL, after air release to be generated is complete, cleared up by microwave, digestion solution is filtered, wash residue with extract, collect cleansing solution, it is settled to predetermined with filtrate mixing.
Wherein, testing sample is fuel incineration residue, soil or mud; Fuel is coal or house refuse, and mud refers to the solids of sedimentation material produced by water and sewage disposal process.Extract is H
3pO
4with the mixed solution of ascorbic acid, H in extract
3pO
4concentration be 0.1 ~ 1.0mol/L, the concentration of ascorbic acid is 0.2 ~ 0.5mol/L.
Airtight microwave digestion can realize clearing up of solid sample fast.Phosphorus and arsenic are congeners, and arsenic can be composed the site of depositing from it and cement out by phosphoric acid efficiently, and phosphoric acid is less relative to other mineral acid oxidisability simultaneously, very micro-on the form impact of arsenic.Ascorbic acid has good inoxidizability, and less to the mutual transformations affect between trivalent arsenic and pentavalent arsenic.In leaching process, preferential and ascorbic acid are had an effect and are not destroyed the valence state of arsenic by the oxidizing substance in lime-ash.Therefore ensure that the harmless extraction of trivalent arsenic and pentavalent arsenic in lime-ash.
(2) trivalent arsenic in mixed liquor step (1) obtained with high performance liquid chromatograph is separated with pentavalent arsenic, wherein, mobile phase is pH value is the potassium dihydrogen phosphate of 6.5 ~ 6.8 and the mixed solution of sodium hydrogen phosphate, flow velocity is 1.0 ~ 1.5mL/min, and chromatographic column selects anion chromatographic column.
Select phosphate can realize arsenate (pentavalent arsenic) as mobile phase to be effectively separated with the quick of arsenous anion (trivalent arsenic).The size of the flow velocity of mobile phase and pH value of solution determine the separating effect of different valence state arsenic, flow velocity increase can make appearance time in advance, but can make simultaneously trivalent arsenic and peak corresponding to pentavalent arsenic more close, therefore, for improving testing efficiency, should make appearance time in advance as far as possible, make the peak shape of trivalent arsenic and pentavalent arsenic clear and legible simultaneously.The flow velocity of mobile phase is preferably 1.0 ~ 1.5mL/min, and within the scope of this, when flow velocity is fast, appearance time slightly shifts to an earlier date, and when flow velocity is slow, appearance time slightly postpones, but trivalent arsenic can be effectively separated with pentavalent arsenic.Control the pH value of mobile phase, the mobile equilibrium of mobile phase intermediate ion (as phosphate radical and hydrogen phosphate etc.) can be realized.The pH value of mobile phase is preferably 6.5 ~ 6.8, and within the scope of this, flowing is on good terms and is realized trivalent arsenic preferably and be separated with the effective of pentavalent arsenic, avoids the interference of heterozygosis ion in solution.
(3) utilize hydride generator successively to reduce to isolated trivalent arsenic and pentavalent arsenic, obtain arsine gas, wherein, the reagent that hydride occurs to use is the first reagent and the second reagent, and the first reagent is HCl, and the second reagent is the KBH containing KOH
4solution.
(4) utilize atomic fluorescence spectrometer to reduce to the arsenic of different valence state the arsine gas obtained to measure, obtain the concentration of trivalent arsenic and pentavalent arsenic in the mixed liquor that step (1) obtains, thus obtain the content of trivalent arsenic and pentavalent arsenic in testing sample.
For making those skilled in the art understand the present invention better, be described in detail below in conjunction with the assay method of specific embodiment to arsenic valence state of the present invention.
Embodiment 1
The assay method of arsenic valence state comprises the steps:
(1) 0.2g testing sample is taken, configuration H
3pO
4with the mixed solution of ascorbic acid as extract, H in extract
3pO
4concentration be 1.0mol/L, the concentration of ascorbic acid is 0.2mol/L; Testing sample is put into Teflon counteracting tank, 20mL extract (solid-to-liquid ratio is 1:100g/mL) is added in testing sample, at room temperature place 15min, after the air release that question response produces is complete, closed digestion tank, put it in microwave dissolver and carry out clearing up (clearing up program is rise to 80 DEG C from room temperature in 10min after, insulation 20min, then naturally cools to room temperature); Digestion solution is filtered, collects filtrate; With extract washing residue more than 3 times, collect cleansing solution, it is mixed with filtrate, and it is to be measured to be settled to 50mL.
(2) parameter of high performance liquid chromatograph is set, chromatographic column selects anion chromatographic column, chromatographic column model is Hamilton PRP-X100 (250mm × 4.1mm i.d., 10 μm), the potassium dihydrogen phosphate of preparation pH=6.8 and the mixed solution (mol ratio of potassium dihydrogen phosphate and sodium hydrogen phosphate is 1:1) of sodium hydrogen phosphate are as mobile phase, flow rate of mobile phase is 1.0mL/min, sample feeding amount is 100 μ L, and the trivalent arsenic in the mixed liquor obtain step (1) is separated with pentavalent arsenic.
(3) hydride generator is utilized successively to reduce to isolated trivalent arsenic and pentavalent arsenic, obtain arsine gas, the reagent that hydride occurs to use is the first reagent and the second reagent, wherein, first reagent to be volume fraction be 7% HCl, the second reagent is KOH and KBH
4mixed solution, wherein, the massfraction of KOH is 0.5%, KBH
4massfraction be 2%.The flow velocity of the first reagent is 7.0mL/min, and the flow velocity of the second reagent is 4.5mL/min.
(4) setting parameter (photomultiplier negative high voltage 250V, total lamp current 70mA, auxiliary lamp electric current 30mA, carrier gas flux 300mL/min, shield gas flow amount 600mL/min) is carried out to atomic fluorescence spectrometer; Utilize atomic fluorescence spectrometer to reduce to the arsenic of different valence state the arsine gas obtained to measure, draw corresponding peak area, the linear equation drawn by typical curve calculates the concentration of trivalent arsenic and pentavalent arsenic in testing sample, and calculates the content of trivalent arsenic and pentavalent arsenic in testing sample further.
Wherein, typical curve obtains in the following way: configure the arsenate (pentavalent arsenic) of five kinds of variable concentrations (being respectively 20ppb, 40ppb, 60ppb, 80ppb and 100ppb) and the mixed standard solution of arsenous anion (trivalent arsenic), corresponding peak area is obtained by the process identical with step (2) ~ (4), draw the typical curve that different valence state arsenic concentration is corresponding with peak area thus, the separation spectral line of the mixed standard solution of five kinds of variable concentrations as shown in Figure 2.
Embodiment 2
H in extract
3pO
4concentration be 1.0mol/L, the concentration of ascorbic acid is 0.5mol/L, other experiment condition and embodiment 1 with.
Embodiment 3
H in extract
3pO
4concentration be 0.5mol/L, the concentration of ascorbic acid is 0.2mol/L, other experiment condition and embodiment 1 with.
Embodiment 4
H in extract
3pO
4concentration be 0.5mol/L, the concentration of ascorbic acid is 0.5mol/L, other experiment condition and embodiment 1 with.
Gather the domestic refuse incineration ash of four different burning power plants, obtain testing sample A, B, C and D respectively.Respectively the content of trivalent arsenic and pentavalent arsenic in testing sample A and B is measured by the method for embodiment 1 and 2, respectively the content of trivalent arsenic and pentavalent arsenic in testing sample C and D is measured by the method for embodiment 3 and 4, obtain the content of trivalent arsenic and pentavalent arsenic in every gram of testing sample.Wherein, each embodiment measures five times to same sample, obtains five groups of test values.Test result is as shown in table 1.
The measurement result of arsenic valence state in table 1 testing sample A, B, C and D
As shown in Table 1, for testing sample A and D, when the concentration of ascorbic acid is 0.2mol/L in extract, just can effectively prevent arsenious oxidation, continue the concentration improving ascorbic acid in extract, little on measurement result impact.And for testing sample B and C, when in extract, the concentration of ascorbic acid is 0.2mol/L, be not enough to prevent arsenious oxidation, make arsenious measured value on the low side, by when in extract, the concentration of ascorbic acid is promoted to 0.5mol/L, the effect preventing trivalent arsenic to be oxidized strengthens, and the trivalent arsenic content recorded significantly improves.In addition, be all less than 5% to the relative standard deviation (Relative Standard Deviation, RSD) of many groups measurement result of testing sample A, B, C and D, the assay method precision of visible arsenic valence state of the present invention is higher.
Utilize standard substance, the accuracy of the assay method of the arsenic valence state of the embodiment of the present invention is verified.Particularly, first in the 0.2g testing sample taken, add the trivalent arsenic standard solution (GBW08666) of the 1ppm (1.0 μ g) of 1mL and 1ppm (1.0 μ g) the pentavalent arsenic standard solution (GBW08667) of 1mL, then add extract.For testing sample A, other test condition and embodiment 1 with, for testing sample B, together, for testing sample C, other test condition and embodiment 4 are together for other test condition and embodiment 2, for testing sample D, other test condition and embodiment 3 are together.Same sample Same Way measures five times, and obtain five groups of test values, in testing sample A, B, C and D, the content of arsenic is known, calculates after average according to group measurement result of five in table 1.Test result is as shown in table 2, and wherein, the recovery=(recording arsenic content in arsenic content-testing sample)/add reference material quality, the accuracy of energy Efficient Evaluation assay method, the recovery, the closer to 100%, illustrates that the accuracy of assay method is higher.
Table 2 adds the measurement result of arsenic valence state in testing sample A, B, C and D after standard substance
As shown in Table 2, after adding standard substance, the recovery of said method is better, is 90.35% ~ 96.15%, illustrates that the inventive method can realize the harmless extraction of trivalent arsenic and pentavalent arsenic in domestic refuse incineration ash, and carry out Accurate Measurement further.In addition, the RSD of many group measurement results is all less than 4%, and the assay method precision further demonstrating arsenic valence state of the present invention is higher.
Embodiment 5
The assay method of arsenic valence state comprises the steps:
(1) 0.2g testing sample is taken, configuration H
3pO
4with the mixed solution of ascorbic acid as extract, H in extract
3pO
4concentration be 0.1mol/L, the concentration of ascorbic acid is 0.2mol/L; Testing sample is put into Teflon counteracting tank, 30mL extract (solid-to-liquid ratio is 1:150g/mL) is added in testing sample, at room temperature place 15min, after the air release that question response produces is complete, closed digestion tank, put it in microwave dissolver and carry out clearing up (clearing up program is rise to 80 DEG C from room temperature in 10min after, insulation 20min, then naturally cools to room temperature); Digestion solution is filtered, collects filtrate; With extract washing residue more than 3 times, collect cleansing solution, it is mixed with filtrate, and it is to be measured to be settled to 100mL.
Subsequent step (2) ~ (4) are same with embodiment 1.
Gather the incineration residue of two kinds of different coals, obtain testing sample E and F respectively.Respectively the content of trivalent arsenic and pentavalent arsenic in testing sample E and F is measured by the method for embodiment 5, five times are measured to same sample, obtains five groups of test values.In addition, utilize standard substance, the accuracy of said determination result is verified.Particularly, first in the 0.2g testing sample taken, add the trivalent arsenic standard solution (GBW08666) of the 2ppm (2.0 μ g) of 1mL and 2ppm (2.0 μ g) the pentavalent arsenic standard solution (GBW08667) of 1mL, add extract again, other test condition and embodiment 5 are together.5 times are measured to same sample, obtains five groups of test values.Above-mentionedly do not add standard substance and to add the measurement result of standard substance as shown in table 3.
The measurement result of table 3 testing sample E and F wherein arsenic valence state when adding/not adding standard substance
As shown in Table 3, after adding standard substance, the recovery of said method is better, is 91.29% ~ 106.13%, and the RSD value of many group measurement results is all less than 4%, illustrates that the inventive method can carry out reasonable analysis and Accurate Measurement to the arsenic morphology in coal incineration residue.
In sum, the content of trivalent arsenic and pentavalent arsenic in method energy Accurate Determining fuel incineration residue (as domestic refuse incineration ash and coal incineration residue) of the present invention, more generally, method of the present invention is also applicable to other solid waste such as soil or mud.For different testing samples, H in extraction agent
3pO
4concentration adjust between 0.1 ~ 1.0mol/L, the concentration of ascorbic acid adjusts between 0.2 ~ 0.5mol/L.Under separation determination condition proposed by the invention, trivalent arsenic can be extracted and is separated well with pentavalent arsenic, and swarming is obvious, appearance time short (within 5min), the accuracy of measurement result is high (90.35% ~ 106.13%), the relative standard deviation of same sample replication is all less than 5%, measures precision high.
Those skilled in the art will readily understand; the foregoing is only preferred embodiment of the present invention; not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (4)
1. an assay method for arsenic valence state, is characterized in that, comprises the steps:
(1) add extract by solid-to-liquid ratio 1:100 ~ 150g/mL to containing in arsenic testing sample, after air release to be generated is complete, cleared up by microwave, digestion solution is filtered, wash residue with extract, collect cleansing solution, it is settled to predetermined with filtrate mixing;
Wherein, extract is H
3pO
4with the mixed solution of ascorbic acid, H in extract
3pO
4concentration be 0.1 ~ 1.0mol/L, the concentration of ascorbic acid is 0.2 ~ 0.5mol/L;
(2) trivalent arsenic in mixed liquor step (1) obtained with high performance liquid chromatograph is separated with pentavalent arsenic;
(3) utilize hydride generator successively to reduce to isolated trivalent arsenic and pentavalent arsenic, obtain arsine gas;
(4) utilize atomic fluorescence spectrometer to reduce to the arsenic of different valence state the arsine gas obtained to measure, obtain the concentration of trivalent arsenic and pentavalent arsenic in the mixed liquor that step (1) obtains, thus obtain the content of trivalent arsenic and pentavalent arsenic in testing sample.
2. the assay method of arsenic valence state as claimed in claim 1, it is characterized in that, in described step (2), mobile phase is pH value is the potassium dihydrogen phosphate of 6.5 ~ 6.8 and the mixed solution of sodium hydrogen phosphate, flow velocity is 1.0 ~ 1.5mL/min, and chromatographic column selects anion chromatographic column.
3. the assay method of arsenic valence state as claimed in claim 1 or 2, is characterized in that, in described step (3), the reagent that hydride occurs to use is the first reagent and the second reagent, and wherein, the first reagent is HCl, and the second reagent is the KBH containing KOH
4solution.
4. the assay method of arsenic valence state as claimed any one in claims 1 to 3, is characterized in that, described is coal incineration residue, domestic refuse incineration ash, soil or mud containing arsenic testing sample.
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| CN110763776B (en) * | 2019-10-18 | 2022-01-28 | 桂林理工大学 | LC-HG-AFS detection method of thioarsenate |
| CN111122765A (en) * | 2020-01-07 | 2020-05-08 | 华北电力大学（保定） | Determination method of arsenic valence state |
| CN111135674A (en) * | 2020-01-07 | 2020-05-12 | 华北电力大学（保定） | Absorption liquid for collecting gas-phase arsenic with different valence states |
| CN114487086A (en) * | 2021-12-22 | 2022-05-13 | 山东师范大学 | Pentavalent arsenic mass spectrum probe and electrospray mass spectrum detection method for measuring pentavalent arsenic |
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