CN204925056U - Electrochemistry prereduction device of HPLC -AFS mercury morphological analysis - Google Patents
Electrochemistry prereduction device of HPLC -AFS mercury morphological analysis Download PDFInfo
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- CN204925056U CN204925056U CN201520652896.1U CN201520652896U CN204925056U CN 204925056 U CN204925056 U CN 204925056U CN 201520652896 U CN201520652896 U CN 201520652896U CN 204925056 U CN204925056 U CN 204925056U
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- afs
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Abstract
The utility model provides an electrochemistry prereduction device of HPLC -AFS mercury morphological analysis, including the same positive pole base member and cathode base of shape, be provided with amberplex between positive pole base member and the cathode base, placed the positive pole gasket between amberplex and the positive pole base member, open porose constitution positive pole pond in the middle of the gasket, place the negative pole gasket between amberplex and the cathode base, opened porose constitution negative pole pond in the middle of the gasket, the outflow pipeline of pipeline through the tee junction high performance liquid chromatography post is passed through in the negative pole pond. Compare with current HPLC -UV -CV -AFS technique, adopt the utility model discloses it is particularly obvious to sensitivity, the detection limit advantage of organic mercury to carry out HPLC -EcVG -AFS's survey, compares 1 low order of magnitude, relative standard deviation <with the HPLC -UV -CV -AFS technique to the detection limit of organic form mercury, 5%.
Description
Technical field
The utility model belongs to and is undertaken the field analyzed, being specifically related to a kind of reduction apparatus for atomic fluorescence spectrometry by spectrum.
Background technology
The Difference In Toxicity of mercury species is very large, and therefore, the morphological analysis of mercury is significant.High performance liquid chromatography-atomic fluorescence spectrophotometry coupling technique (HPLC-AFS) is the common method that current mercury morphological analysis adopts.This technology adopts HPLC isolation technics by inorganic mercury (Hg
2+), methyl mercury (HgCH
3 +), ethyl mercury (HgC
2h
5 +), phenyl mercury (HgC
6h
5 +) etc. 4 kinds of conventional mercury shapes be separated, then detected by AFS technology.Conventional AFS technology adopts the cold steam of chemical method that (coldvaporgeneration occurs, CV method) mercury element is realized atomization by potassium borohydride-acid system electronation to mode but CV technology is extremely low to organomercurial atomization efficiency, so after HPLC technology realizes different shape separation, be typically employed in the technology (i.e. HPLC-UV-CV-AFS) of line ultraviolet digestion, organic mercury is decomposed into inorganic mercury, then again by CV technology atomization, atomic fluorescence method detects.
Prior art (HPLC-UV-CV-AFS) is still on the low side to organomercurial ultraviolet digestion efficiency, cause organic mercury detection limit on the low side, and CV technology still needs the reductive agent of this instability of potassium borohydride, while higher to reagent purity requirement, also need matching while using, analysis efficiency is lower.The utility model adopts electrochemical reduction steam generation technique (Electrochemicalcoldvaporgeneration, EcVG) technology to replace ultraviolet digestion technology.After HPLC realizes the separation of different mercury shape, directly realize organomercurial atomization (HPLC-EcVG-AFS) by EcVG technology, atomic fluorescence method detects.
Utility model content
In order to solve the technical matters that this area exists, the purpose of this utility model is to provide a kind of galvanochemistry prereduction device of HPLC-AFS mercury morphological analysis.
The technical scheme realizing the utility model object is:
A kind of galvanochemistry prereduction device for HPLC-AFS mercury morphological analysis, it is connected through threeway with the outflow conduit of performance liquid chromatographic column, described galvanochemistry prereduction device comprises the identical anode substrate of shape and cathode base, amberplex is provided with between anode substrate and cathode base, be placed with anode pad between described amberplex and anode substrate, have hole in the middle of described anode pad and form anode pool; Be placed with negative electrode pad between described amberplex and cathode base, have hole in the middle of described negative electrode pad and form cathode pool; Described cathode pool connects the outflow conduit of performance liquid chromatographic column through threeway by pipeline.
Further, described anode substrate and cathode base are teflon material, anode substrate are provided with anolyte entrance and anolyte outlet, and anolyte entrance is connected with peristaltic pump.Entrance pipe and export pipeline are all placed in sulfuric acid closed circuit and realize circulation.
Wherein, described anode substrate is provided with anode, described anode is platinum electrode; Described cathode base is provided with negative electrode, and described negative electrode is glass-carbon electrode.
Wherein, described cathode base is provided with catholyte entrance and catholyte outlet, described catholyte entrance connects the outflow conduit of performance liquid chromatographic column by pipeline, and described catholyte outlet is connected to the reaction block of atomic fluorescence spectrophotometer.
The AFS instruments such as the device that the utility model proposes can be connected to commercially available atomic fluorescence spectrophotometer, and such as Beijing Haiguang Instrument Co., Ltd. produces AFS-9800, the AFS-820 that Beijing Jitian Instrument Co., Ltd. produces.It is carrier gas that the reaction block of atomic fluorescence spectrophotometer normally passes into argon gas, and passes into sample, current-carrying (acid) and reductive agent (such as potassium borohydride) and react, and the atomic state mercury that will be produced by argon gas is loaded into atomizer.Adopt device of the present utility model, do not react in reaction block during detection, just take the atomic state mercury of electrochemical reduction formation with carrier gas out of.
Wherein, the reaction block of described atomic fluorescence spectrophotometer also connects the pipeline of input carrier gas argon gas, and the reaction block of described atomic fluorescence spectrophotometer is connected with the gas-liquid separator of atomic fluorescence spectrophotometer.
Apply the step that device of the present utility model carries out galvanochemistry prereduction to comprise:
1) sample containing mercury enters performance liquid chromatographic column, according to the difference of retention time, is separated by the mercury of different shape through performance liquid chromatographic column (HPLC);
2), after the mercury be separated through performance liquid chromatographic column mixes with cathode-supported electrolyte, be input in the cathode chamber of electrochemical circulation pool by peristaltic pump, become mercury vapour through electrolytic reduction;
3) mercury vapour realizes gas-liquid separation in gas-liquid separator, is loaded into the atomizer of atomic fluorescence spectrophotometer, realizes the quantitative test of mercury species by carrier gas argon gas.
Wherein, described containing in the sample of mercury, the form of mercury is Hg
2+, HgCH
3 +, HgC
2h
5 +, HgC
6h
5 +in one or more.
With HPLC, separate according to different mercury shape disengaging time difference.
Preferably, described step 2) in, adopt constant-current electrolysis, current density is 0.1 ~ 0.55A/cm
2.More preferably current density is 0.54A/cm
2.
Wherein, described step 2) in, the supporting electrolyte of the negative electrode of electrochemical circulation pool is the sulfuric acid solution of 0.1 ~ 0.5mol/L; The electrolytic solution of the anode of electrochemical circulation pool is the sulfuric acid solution of 0.1 ~ 0.5mol/L.Preferably, the supporting electrolyte of the negative electrode of electrochemical circulation pool is the sulfuric acid solution of 0.5mol/L; The electrolytic solution of the anode of electrochemical circulation pool is the sulfuric acid solution of 0.5mol/L.
Wherein, in mercury species analytic process, the circulate electrolyte of anode uses, and cathode waste stream is discharged by peristaltic pump.
Described step 3) in the flowing velocity of carrier gas be 300 ~ 900mLmin
-1.Preferably, flow rate of carrier gas is 500mLmin
-1.
The beneficial effects of the utility model are:
Compared with existing HPLC-UV-CV-AFS technology, device of the present utility model is adopted to carry out HPLC-EcVG-AFS mensuration, particularly evident to organomercurial sensitivity, detection limit advantage, to Hg
2+, HgCH
3 +, HgC
2h
5 +, HgC
6h
5 +detection limit reach 2.8ng/L, 1.9ng/L, 2.4ng/L and 3.8ng/L respectively, to detection limit about low 1 order of magnitude compared with HPLC-UV-CV-AFS technology of organic form mercury, relative standard deviation <5% (n=6).Meanwhile, there is the advantage not needing the reductive agents such as potassium borohydride, broken away from the dependence to reagent purity, stability.
Accompanying drawing explanation
Fig. 1 is the structure diagram of the utility model device.
Fig. 2 is the structure diagram of the utility model electrochemical circulation pool.
Fig. 3 is that embodiment 1 cathode chamber length and width are fixed, and thickness is that the electrochemical circulation pool that is assembled into of two kinds of silicone rubber plates of 0.05cm (cathode chamber volume 0.14mL) and 0.1cm (cathode chamber volume 0.28mL) is on the impact (for methyl mercury) of measurement result.
Fig. 4 (a) is for embodiment 2 is to 2 μ g/L inorganic mercury (Hg
2+) 6 measurement results, Fig. 4 (b) is 2 μ g/L inorganic mercury (Hg
2+) typical curve,
Fig. 5 (a) is 2 μ g/L methyl mercuries, 6 measurement results, and Fig. 5 (b) is the typical curve under 2 μ g/L methyl mercury measures 1.5A for 6 times.
In figure: 1, HPLC chromatographic column, 2, anode fluid channel, 3, catholyte pipeline, 4, peristaltic pump, 5, power supply, 6,0.5mol/L sulfuric acid pipeline, 7. reaction block, 8, cathode waste stream pipeline, 9, gas-liquid separator, 10, amberplex, 11, platinum electrode, 12, glass-carbon electrode, 13, carrier gas channel, 14, mobile phase and sample inlet, 15, Hg steam (vapor) outlet, 16, silicone rubber plate, 17, anolyte entrance, 18, anolyte outlet, 19, catholyte entrance, 20, catholyte outlet, 21, PTFE matrix.
Embodiment
Following examples for illustration of the utility model, but are not used for limiting scope of the present utility model.
In embodiment, if no special instructions, the means adopted are the technological means of this area routine.
Embodiment 1
As Fig. 1 and Fig. 2, a kind of galvanochemistry prereduction device for HPLC-AFS mercury morphological analysis, it is connected with the outflow conduit of C18 performance liquid chromatographic column (ZORBAXXDB-C18 post), this galvanochemistry prereduction device is with PTFE matrix 21, silicone rubber plate 16, the electrochemical circulation pool that amberplex 10 (Nafion film) assembles, specifically comprise the identical PTFE anode substrate of shape and cathode base, amberplex 10 is provided with between anode substrate and cathode base, the anode pad that silicone rubber plate 16 is made is placed with between amberplex 10 and anode substrate, have slot in the middle of silicone rubber plate 16 and form anode chamber, be placed with anode pad between amberplex 10 and cathode base, pad central aperture forms cathode chamber, cathode chamber connects the outflow conduit of performance liquid chromatographic column by pipeline.
Anode substrate is provided with anolyte entrance 17 and anolyte outlet 18, anolyte entrance 17 connects peristaltic pump 4, the closed circuit that entrance pipe and export pipeline are all placed in 0.5mol/L sulfuric acid realizes circulation, is connected with 0.5mol/L sulfuric acid pipeline 6 in this closed circuit.Anode substrate embeds platinum electrode 11 for anode, cathode base embeds glass-carbon electrode 12 as negative electrode.
Described cathode base is provided with catholyte entrance 19 and catholyte outlet 20, described catholyte entrance 19 is connected the outflow conduit of HPLC chromatographic column 1 with pipeline through threeway, the import of HPLC chromatographic column 1 is mobile phase and sample inlet 14, and described catholyte outlet is connected to the reaction block 7 of atomic fluorescence spectrophotometer (sea light AFS-9800).The reaction block 7 of atomic fluorescence spectrophotometer also connects the carrier gas channel 13 of input argon gas, and the reaction block 7 of atomic fluorescence spectrophotometer is connected with the gas-liquid separator 9 of atomic fluorescence spectrophotometer, and the Hg steam (vapor) outlet 15 of gas-liquid separator 9 connects AFS.
The hole formed objects that the middle slot of silicone rubber plate 16 of anode and negative electrode pad are opened.Arranging cathode chamber long and wide is 7cm and 0.4cm, and thickness is 0.05cm (cathode chamber volume 0.14mL).
Atomic fluorescence spectrophotometer is that Beijing Haiguang Instrument Co., Ltd. produces AFS-9800.HPLC part is identical with operation with the configuration of HPLC-UV-CV-AFS commercialization instrument.
Adopt the device of the present embodiment, HPLC mobile phase: 3% acetonitrile+0.5% ammonium acetate+0.03%2-mercaptoethanol, adopt 1.5A Faradaic current to measure, the results are shown in Table 1 and Fig. 4, Fig. 5.Fig. 4 (a), (b) are 2ppb inorganic mercury (Hg
2+) measure and typical curve under different electric current, Fig. 5 (a), (b) they are that 2ppb methyl mercury measures for 6 times and typical curve under 1.5A. for 6 timesResult shows: adopt device of the present utility model, and under 1.5A Faradaic current, calibration curve meets the requirement of analysis.
Table 1, AFS analysis indexes
Experimental result shows that method of the present utility model is particularly evident to organomercurial sensitivity, detection limit advantage, to Hg
2+, HgCH
3 +, HgC
2h
5 +, HgC
6h
5 +detection limit reach 2.8ng/L, 1.9ng/L, 2.4ng/L and 3.8ng/L respectively, to detection limit about low 1 order of magnitude compared with HPLC-UV-CV-AFS technology of organic form mercury, relative standard deviation <5% (n=6).
Embodiment 2
As Fig. 1, a kind of galvanochemistry prereduction device for HPLC-AFS mercury morphological analysis, it is connected with the outflow conduit of C18 performance liquid chromatographic column (ZORBAXXDB-C18 post), this galvanochemistry prereduction device is with PTFE matrix 21, silicone rubber plate 16, the electrochemical circulation pool that amberplex 10 assembles, specifically comprise the identical PTFE anode substrate of shape and cathode base, amberplex 10 is provided with between anode substrate and cathode base, the anode pad that silicone rubber plate 16 is made is placed with between amberplex 10 and anode substrate, have slot in the middle of silicone rubber plate 16 and form anode chamber, be placed with anode pad between amberplex 10 and cathode base, pad central aperture forms cathode chamber, cathode chamber connects the outflow conduit of performance liquid chromatographic column by pipeline.
In the present embodiment, the hole formed objects that the middle slot of silicone rubber plate 16 of anode and negative electrode pad are opened, long and wide is 7cm and 0.4cm, and thickness is 0.1cm (cathode chamber volume 0.28mL) two kinds.For methyl mercury, test electrochemical circulation pool that two kinds of silicone rubber plates are assembled into the impact (Fig. 3) of mercury vapour luminous efficiency, wherein the sensitivity of 0.14mL volume is higher.The film that cation-exchange membrane adopts Shandong Tianwei Membrane Technology Co., Ltd. to produce, reaches the Detection results identical with embodiment 1.
Other parts of device are with embodiment 1.
Although above done detailed description to the utility model with a general description of the specific embodiments, on the utility model basis, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements on the basis of not departing from the utility model spirit, all belong to the scope that the utility model is claimed.
Claims (5)
1. the galvanochemistry prereduction device for HPLC-AFS mercury morphological analysis, it is connected with the outflow conduit of performance liquid chromatographic column, it is characterized in that, described galvanochemistry prereduction device comprises the identical anode substrate of shape and cathode base, amberplex is provided with between anode substrate and cathode base, be placed with anode pad between described amberplex and anode substrate, have hole in the middle of described anode pad and form anode pool; Be placed with negative electrode pad between described amberplex and cathode base, have hole in the middle of described negative electrode pad and form cathode pool; Described cathode pool connects the outflow conduit of performance liquid chromatographic column through threeway by pipeline.
2. galvanochemistry prereduction device according to claim 1, it is characterized in that, described anode substrate and cathode base are teflon material, anode substrate are provided with anolyte entrance and anolyte outlet, and anolyte entrance is connected with peristaltic pump.
3. galvanochemistry prereduction device according to claim 1, is characterized in that, described anode substrate is provided with anode, and described anode is platinum electrode; Described cathode base is provided with negative electrode, and described negative electrode is glass-carbon electrode.
4. according to the arbitrary described galvanochemistry prereduction device of claims 1 to 3, it is characterized in that, described cathode base is provided with catholyte entrance and catholyte outlet, described catholyte entrance connects the outflow conduit of performance liquid chromatographic column by pipeline, and described catholyte outlet is connected to the reaction block of atomic fluorescence spectrophotometer.
5. galvanochemistry prereduction device according to claim 4, it is characterized in that, the reaction block of described atomic fluorescence spectrophotometer also connects the pipeline of input carrier gas argon gas, and the reaction block of described atomic fluorescence spectrophotometer is connected with the gas-liquid separator of atomic fluorescence spectrophotometer.
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|---|---|---|---|
| CN201520652896.1U CN204925056U (en) | 2015-08-26 | 2015-08-26 | Electrochemistry prereduction device of HPLC -AFS mercury morphological analysis |
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| CN201520652896.1U CN204925056U (en) | 2015-08-26 | 2015-08-26 | Electrochemistry prereduction device of HPLC -AFS mercury morphological analysis |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105092763A (en) * | 2015-08-26 | 2015-11-25 | 北京市理化分析测试中心 | Electrochemical pre-reduction method and device for mercury speciation analysis by HPLC-AFS (high performance liquid chromatography and atomic fluorescence spectroscopy) |
-
2015
- 2015-08-26 CN CN201520652896.1U patent/CN204925056U/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105092763A (en) * | 2015-08-26 | 2015-11-25 | 北京市理化分析测试中心 | Electrochemical pre-reduction method and device for mercury speciation analysis by HPLC-AFS (high performance liquid chromatography and atomic fluorescence spectroscopy) |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20151230 Termination date: 20160826 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |