CN101236183A - Ion chromatograph -double anode electrochemical hydride generation atomic fluorescent on-line combined system - Google Patents
Ion chromatograph -double anode electrochemical hydride generation atomic fluorescent on-line combined system Download PDFInfo
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- CN101236183A CN101236183A CNA2008100598151A CN200810059815A CN101236183A CN 101236183 A CN101236183 A CN 101236183A CN A2008100598151 A CNA2008100598151 A CN A2008100598151A CN 200810059815 A CN200810059815 A CN 200810059815A CN 101236183 A CN101236183 A CN 101236183A
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Abstract
The invention relates to an ion chromatography-binode electrochemical hydride generation atomic fluorescence on-line combined system, which comprises a liquid chromatography pump, an admission valve, an ion chromatographic column, a three-way connecting device, a peristaltic pump, a binode electrochemical hydride generator, a four-way connecting device, a gas-liquid separator and an atomic fluorescence photometer. Element compounds of different forms in a sample are separated on the ion chromatographic column, the separated components are reduced to gaseous hydride on the binode electrochemical hydride generator, the gaseous hydride after undergoing gas liquid separation through the gas-liquid separator is led into the atomic fluorescence photometer by carrier gas for detection, and signals are recorded and processed by a self-developed work station. The ion chromatography-binode electrochemical hydride generation atomic fluorescence on-line combined system successfully realizes effectively converting the element compounds of different forms separated by the ion chromatographic column into hydride on line, and introduces an atomic fluorescence detection system on line, thereby establishing a simple, quick, sensitive, accurate, economical and reliable new technologic platform for element form analysis.
Description
Technical field
The present invention relates to the combined system of chemical analysis instrument, particularly the ion chromatograph-double anode electrochemical hydride generation atomic fluorescent on-line coupled system.
Background technology
The toxicity of element and biological importance all depend on its chemical form, the form that many elements are different and the toxicity of valence state have very big difference, and these elements comprise arsenic, selenium, lead, bismuth etc., are example with arsenic, the toxicity difference of different shape arsenic, inorganic arsenic (comprises trivalent arsenic As
3+With pentavalent arsenic As
5+) the toxicity maximum, the toxicity of the arsenic that methylates (comprising monomethyl arsenic MMA and dimethyl arsenic DMA) is less, and that arsenic betaine (AsB), arsenocholine (AsC), arsenic sugar (AsS), arsenic fat (AsL) etc. are considered to toxicity usually is very low or nontoxic.Thereby the mensuration of element total amount can not satisfy the research needs in fields such as environmental science, life science, medical and health, develops easy quick, sensitive and accurate Elemental Speciation Analysis assay method and is very important.
At present, the method that is used for Elemental Speciation Analysis comparatively effectively detects the technology of coupling mutually based on chromatographic resolution with elemental characteristic, wherein high performance liquid chromatography and inductivity coupled plasma mass spectrometry (HPLC-ICPMS) coupling technique occupies critical role with its high sensitivity, low detection limit and multielement detectability in morphological analysis, but the equilibration period of traditional quadrupole rod ICPMS is longer, work efficiency is restricted, cost an arm and a leg in addition, the operating cost height, thereby limited the penetration and promotion of this coupling technique.In recent years, high performance liquid chromatography and atomic fluorescence coupling (HPLC-AFS) technology be used for Elemental Speciation Analysis extremely researchers pay close attention to, its sensitivity and detection limit can compare favourably with HPLC-ICPMS, and cost is low, the efficient height, react but all use traditional chemical reducing agent (as potassium borohydride, sodium borohydride etc.) to carry out hydride, chemical reducing agent (potassium borohydride, sodium borohydride etc.) in use less stable has influenced the precision of assay determination, and brings pollution to environment.So far, do not see that the electrochemical hydride generator is used for the coupling technique report of interface between HPLC and the AFS.
With the interface of Binode electro-chemistry hydride generator, can become the strong instrument of Elemental Speciation Analysis as chromatography of ions and atomic fluorescence spectrophotometry coupling technique.The key that realizes this coupling technique is the appropriate design of interface, in Interface design, how to realize timely and effectively online hydride, and the online introducing atomic fluorescence detection system of being converted into of the analyte component that chromatographic column is separated, become the key issue of ion chromatograph-double anode electrochemical hydride generation atomic fluorescent on-line coupled system.
Summary of the invention
The invention provides a kind of ion chromatograph-double anode electrochemical hydride generation atomic fluorescent on-line coupled system, set up the new technical platform of easy quick, sensitive and accurate, economic and reliable for Elemental Speciation Analysis.
Ion chromatograph-double anode electrochemical hydride generation atomic fluorescent on-line coupled system of the present invention, an import in the negative electrode threeway input interface of chromatography of ions chromatographic column outlet and Binode electro-chemistry hydride generator is connected, simultaneously catholyte is connected by another import in the negative electrode threeway input interface of peristaltic pump and Binode electro-chemistry hydride generator, the negative electrode output interface of Binode electro-chemistry hydride generator is connected with a import in the four-way interface, and gas (Ar) and combustion gas (H are carried in two imports in addition in the four-way interface respectively
2), outlet in the four-way interface is connected with the import of gas-liquid separator, the lower end outlet of gas-liquid separator is connected with waste liquid bottle by peristaltic pump, and the upper end outlet of gas-liquid separator is connected with the atomic fluorescence detection system, and the atomic fluorescence signal is connected with computing machine by signal wire.The IO interface that has anolyte on two anodic site housings of Binode electro-chemistry hydride generator system respectively, the threeway input interface and the output interface that is connected assay determination sample component checkout equipment that have assay determination sample component and catholyte on the housing in cathodic area, two cation exchange resin membranes are attached to two sides of negative electrode respectively, negative electrode threeway input interface, negative electrode, negative electrode output interface three is in the same center line, the volume of anodic site is 55 * 13 * 10mm, the titanium silk of long 110mm diameter 2mm places the centre of anodic site, the cathodic area volume is 55 * 13 * 2mm, 53 * 13 * 1.8mm lead metal plate negative electrode places the centre in cathodic area, two anodes are independently-powered respectively by two power supplys, and the current density of control cathode is 0.5Acm
-2About.
Advantage of the present invention and effect: Binode electro-chemistry hydride takes place the hydride of some elements (as arsenic, selenium, tellurium etc.) can take place, and needn't take place by chemical hydride, has chemical hydride simultaneously identical sensitivity and the reappearance of Geng Gao take place.By the separation of chromatography of ions, can realize the form and the Determination of Different Valence States of some elements (as arsenic, selenium, tellurium etc.), solve the analysis that traditional atomic fluorescence and other atomic spectrum can't be realized.
Description of drawings
Fig. 1 is an ion chromatograph-double anode electrochemical hydride generation atomic fluorescent on-line coupled system schematic flow sheet of the present invention.
Fig. 2 is the standard model (As of ion chromatograph-double anode electrochemical hydride generation atomic fluorescent on-line coupled system
3+, As
5+, MMA, DMA) signal peak
Fig. 3 is actual sample (the I type pulp devitalization material) signal peak of ion chromatograph-double anode electrochemical hydride generation atomic fluorescent on-line coupled system
Be labeled as among Fig. 1:
1-moving phase; The 2-liquid chromatography pump; The 3-sampling valve; The 4-chromatographic column; 5-negative electrode threeway input interface; The 6-catholyte; The 7-Binode electro-chemistry hydride generator; 8-negative electrode output interface; 9-four-way interface; The 10-argon gas; 11-hydrogen; The 12-gas-liquid separator; The 13-atomic fluorescence spectrophotometer; 14-computing machine and workstation; The 15-peristaltic pump; The 16-waste liquid bottle; 17,17 '-the anolyte input interface; 18,18 '-the anolyte output interface; The 19-anolyte; The 20-peristaltic pump.
Embodiment
As shown in Figure 1, moving phase 1 is carried by liquid chromatography pump 2, analyzed sample is by sampling valve 3 quantitative sample injections, component after chromatographic column 4 is separated enters the cathodic area by an import in the Binode electro-chemistry hydride generator negative electrode threeway input interface 5, catholyte 6 enters the cathodic area by another import that peristaltic pump 15 is transported in the negative electrode threeway input interface simultaneously, anolyte 19 is transported to anolyte input interface 17 by peristaltic pump 20,17 ' enter the anodic site, from anolyte output interface 18,18 ' turn back to anolyte 19 to recycle or be discharged into waste liquid bottle 16, component after the chromatographic resolution is reduced into gaseous hydride in the Binode electro-chemistry hydride generator cathodic area, gaseous hydride that is generated and catholyte are transported to a import in the four-way interface 9, carrier gas simultaneously (Ar) 10 and combustion gas (H by the negative electrode output interface 8 of Binode electro-chemistry hydride generator
2) 11 import catholyte, gaseous hydride, carrier gas (Ar), combustion gas (H respectively by in addition two imports in the four-way interface
2) import that is transported to gas-liquid separator 12 by the output interface of four-way interface enters gas-liquid separator and carry out gas-liquid separation, waste liquid is discharged into waste liquid bottle 16 by peristaltic pump 15, gaseous hydride, carrier gas (Ar), combustion gas (H by the lower end outlet of gas-liquid separator
2) be transported to atomic fluorescence spectrophotometer 13 (after the secondary gas-liquid separation) by the outlet of the upper end of gas-liquid separator and detect, signal is by computing machine and workstation1 4 records and handle.
Select the DX-100T ion chromatograph of U.S. Dai An company (Dionex) for use, IonPac AG14 (50mm * 4mm * 9 μ m) guard column and IonPac AS14 (250mm * 4mm * 9 μ m) analytical column are with 6.0mmolL
-1PH 6.20NH
4H
2PO
4Be leacheate, the leacheate flow velocity is 1.5mLmin
-1, sample size 100 μ L; Homemade Binode electro-chemistry hydride generator, the volume of anodic site is 55 * 13 * 10mm, the titanium silk of long 110mm diameter 2mm places the centre of anodic site, the cathodic area volume is 55 * 13 * 2mm, 53 * 13 * 1.8mm lead metal plate negative electrode places the centre in cathodic area, two anodes are independently-powered respectively by two SR-20A Ha Shi groove power source specials (manufacturing of scientific instrument factory of Taishan City SAST), and Faradaic current is that (current density of current stabilization, negative electrode is 0.5Acm to 3.5A
-2About), the electrolytic solution sulfuric acid concentration is 0.50molL
-1, the flow of anolyte is 4mLmin
-1(recycling), the flow of catholyte are 1.5mLmin
-1Provide hydrogen, hydrogen flowing quantity 80mLmin by CYH-500 hydrogen generator (Beijing is newly created space instrument plant and made)
-1AFS-830 two pass atomic fluorescence spectrophotometer (Beijing Jitian Instrument Co., Ltd.'s manufacturing), high strength as hollow cathode lamp, lamp current (primary/secondary) 30/30mA, negative high voltage 290V, 780 ℃ of atomization temperatures, carrier gas flux 300mLmin
-1, shield gas flow amount 500mLmin
-1Under this experiment condition, with ion chromatograph-double anode electrochemical hydride generation atomic fluorescent on-line coupled system of the present invention, can be to trivalent inorganic arsenic (As
3+), pentavalent inorganic arsenic (As
5+), four kinds of different arsenic morphology compound separation of monomethyl arsenic (MMA) and dimethyl arsenic (DMA) and the detection limit realized be respectively 3.04 μ gL
-1, 4.27 μ gL
-1, 3.97 μ gL
-1, 9.30 μ gL
-1
Claims (3)
1. ion chromatograph-double anode electrochemical hydride generation atomic fluorescent on-line coupled system, the chromatographic column outlet that it is characterized in that chromatography of ions is connected with a import in the negative electrode threeway input interface of Binode electro-chemistry hydride generator, simultaneously electrolytic solution sulfuric acid is connected by another import in the negative electrode threeway input interface of peristaltic pump and Binode electro-chemistry hydride generator, the negative electrode output interface of Binode electro-chemistry hydride generator is connected with a import in the four-way interface, and gas (Ar) and combustion gas (H are carried in two imports in addition in the four-way interface respectively
2), outlet in the four-way interface is connected with the import of gas-liquid separator, the lower end outlet of gas-liquid separator is connected with waste liquid bottle, and the upper end outlet of gas-liquid separator is connected with the atomic fluorescence detection system, and the atomic fluorescence signal is connected with computing machine by signal wire.
2. ion chromatograph-double anode electrochemical hydride generation atomic fluorescent on-line coupled system according to claim 1, it is characterized in that the hydride of some elements (as arsenic, selenium, tellurium etc.) takes place to take place Binode electro-chemistry hydride, and needn't take place by chemical hydride, have chemical hydride simultaneously identical sensitivity and the reappearance of Geng Gao take place.
3. ion chromatograph-double anode electrochemical hydride generation atomic fluorescent on-line coupled system according to claim 1, it is characterized in that separation by chromatography of ions, can realize the form and the Determination of Different Valence States of some elements (as arsenic, selenium, tellurium etc.), solve the analysis that traditional atomic fluorescence and other atomic spectrum can't be realized.
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| CN102033103A (en) * | 2010-10-26 | 2011-04-27 | 中国地质大学（武汉） | Mercury morphological analysis method based on liquid cathode discharge and mercury vapor generating device |
| CN102053130A (en) * | 2010-12-07 | 2011-05-11 | 浙江大学 | Ion chromatography-electrochemical derivative-fluorescence analysis system |
| CN101650350B (en) * | 2009-09-14 | 2012-05-23 | 华北电力大学（保定） | Instrument coupled speciation measuring method of gaseous arsenic compound |
| CN102520090A (en) * | 2011-12-20 | 2012-06-27 | 苏州硒谷科技有限公司 | Method for determining selenium form in selenium-rich health product |
| CN102519922A (en) * | 2011-11-18 | 2012-06-27 | 北京锐光仪器有限公司 | Atomic fluorescence device for simultaneously determining multiple elements and determination method thereof |
| CN102520104A (en) * | 2011-12-20 | 2012-06-27 | 苏州硒谷科技有限公司 | Method for determination of form of selenium in selenium-rich plant material |
| CN102519933A (en) * | 2011-12-20 | 2012-06-27 | 苏州硒谷科技有限公司 | Method for determining form of selenium in selenium-enriched edible fungi |
| CN104678027A (en) * | 2015-02-04 | 2015-06-03 | 天津科技大学 | Rapid multi-mode element speciation analysis pretreatment system |
| CN105300755A (en) * | 2015-09-15 | 2016-02-03 | 北京普析通用仪器有限责任公司 | Coupling device of hydride generator and microwave plasma mass spectrometer |
| CN105699504A (en) * | 2016-01-15 | 2016-06-22 | 青岛检验检疫技术发展中心 | Real-time detection device for online oxidation reduction of substance prone to oxidation |
| CN106248824A (en) * | 2016-07-08 | 2016-12-21 | 德州职业技术学院 | High performance liquid chromatography atomic fluorescence combination analysis system mathematic model and data processing method |
| CN106290603A (en) * | 2016-07-19 | 2017-01-04 | 浙江树人大学 | A kind of utilize Vavle switching method to detect the inorganic anion in plant, organic acid and the method for three kinds of phytochemicalss and application simultaneously |
| CN107894511A (en) * | 2017-10-27 | 2018-04-10 | 河北莱博瑞特电子科技有限公司 | A kind of Elemental Speciation Analysis instrument |
| CN109655573A (en) * | 2017-10-10 | 2019-04-19 | 戴安公司 | Quick start ion chromatography system and method |
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| CN2788181Y (en) * | 2004-07-02 | 2006-06-14 | 中国科学院生态环境研究中心 | Highly-efficient liquid phase chromatogram-atomic fluorescence spectrum arsenic shape analysis on-line coupled system |
| US20090298183A1 (en) * | 2005-12-14 | 2009-12-03 | Purnendu Kumar Dasgupta | Method and apparatus for analyzing arsenic concentrations using gas phase ozone chemiluminescence |
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2008
- 2008-02-04 CN CN 200810059815 patent/CN101236183B/en not_active Expired - Fee Related
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| CN101650350B (en) * | 2009-09-14 | 2012-05-23 | 华北电力大学（保定） | Instrument coupled speciation measuring method of gaseous arsenic compound |
| CN102033103A (en) * | 2010-10-26 | 2011-04-27 | 中国地质大学（武汉） | Mercury morphological analysis method based on liquid cathode discharge and mercury vapor generating device |
| CN102053130A (en) * | 2010-12-07 | 2011-05-11 | 浙江大学 | Ion chromatography-electrochemical derivative-fluorescence analysis system |
| CN102519922A (en) * | 2011-11-18 | 2012-06-27 | 北京锐光仪器有限公司 | Atomic fluorescence device for simultaneously determining multiple elements and determination method thereof |
| CN102519922B (en) * | 2011-11-18 | 2014-03-05 | 北京锐光仪器有限公司 | Atomic fluorescence device for simultaneously determining multiple elements and measurement method thereof |
| CN102520090A (en) * | 2011-12-20 | 2012-06-27 | 苏州硒谷科技有限公司 | Method for determining selenium form in selenium-rich health product |
| CN102520104A (en) * | 2011-12-20 | 2012-06-27 | 苏州硒谷科技有限公司 | Method for determination of form of selenium in selenium-rich plant material |
| CN102519933A (en) * | 2011-12-20 | 2012-06-27 | 苏州硒谷科技有限公司 | Method for determining form of selenium in selenium-enriched edible fungi |
| CN104678027A (en) * | 2015-02-04 | 2015-06-03 | 天津科技大学 | Rapid multi-mode element speciation analysis pretreatment system |
| CN105300755A (en) * | 2015-09-15 | 2016-02-03 | 北京普析通用仪器有限责任公司 | Coupling device of hydride generator and microwave plasma mass spectrometer |
| CN105699504A (en) * | 2016-01-15 | 2016-06-22 | 青岛检验检疫技术发展中心 | Real-time detection device for online oxidation reduction of substance prone to oxidation |
| CN106248824A (en) * | 2016-07-08 | 2016-12-21 | 德州职业技术学院 | High performance liquid chromatography atomic fluorescence combination analysis system mathematic model and data processing method |
| CN106248824B (en) * | 2016-07-08 | 2018-11-23 | 德州职业技术学院 | High performance liquid chromatography-atomic fluorescence combination analysis system mathematic model and data processing method |
| CN106290603A (en) * | 2016-07-19 | 2017-01-04 | 浙江树人大学 | A kind of utilize Vavle switching method to detect the inorganic anion in plant, organic acid and the method for three kinds of phytochemicalss and application simultaneously |
| CN106290603B (en) * | 2016-07-19 | 2019-03-12 | 浙江树人大学 | A kind of method and application detecting inorganic anion in plant, organic acid and three kinds of phytochemicals simultaneously using Vavle switching method |
| CN109655573A (en) * | 2017-10-10 | 2019-04-19 | 戴安公司 | Quick start ion chromatography system and method |
| US11105782B2 (en) | 2017-10-10 | 2021-08-31 | Dionex Corporation | Fast startup ion chromatography system and methods |
| CN107894511A (en) * | 2017-10-27 | 2018-04-10 | 河北莱博瑞特电子科技有限公司 | A kind of Elemental Speciation Analysis instrument |
| CN107894511B (en) * | 2017-10-27 | 2023-09-15 | 河北莱博瑞特电子科技有限公司 | Elemental morphology analyzer |
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