CN111562239A - Multi-position automatic photochemical steam generation device and working method thereof - Google Patents
Multi-position automatic photochemical steam generation device and working method thereof Download PDFInfo
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- CN111562239A CN111562239A CN202010432170.2A CN202010432170A CN111562239A CN 111562239 A CN111562239 A CN 111562239A CN 202010432170 A CN202010432170 A CN 202010432170A CN 111562239 A CN111562239 A CN 111562239A
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
- B01J19/123—Ultra-violet light
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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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/3103—Atomic absorption analysis
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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
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
Abstract
The invention relates to the technical field of chemical detection, and discloses a multi-position automatic photochemical steam generating device and a working method thereof. Namely, on one hand, in the multi-position photochemical reaction mechanism, by designing the ultraviolet lamp into a ring shape and arranging a plurality of sample bottles around the ring-shaped central ring of the ring-shaped ultraviolet lamp at intervals by the sample rack, and rotating the sample bottles around the annular center by the rotating platform to allow the samples to simultaneously react with photochemical vapor under the irradiation of ultraviolet light, thereby greatly improving the flux of the measured sample, on the other hand, in the automatic headspace sampling mechanism, through the configuration of the rotary platform, the vertical expansion bracket, the horizontal bracket, the purging air inlet pipeline, the air inlet needle tube, the air outlet needle tube and the purging air outlet pipeline, the quartz bottle headspace area can be communicated with the carrier gas source and the atomic spectrum excitation source one by one, the purpose of adopting gas purging sample injection to replace the traditional flow injection sample injection is realized, so that the interference of memory effect and water vapor can be eliminated, and the detection sensitivity is greatly improved.
Description
Technical Field
The invention belongs to the technical field of chemical detection, relates to the application fields of analytical chemistry, environmental chemistry, in-situ detection, laboratory detection and the like, and particularly relates to a high-flux, high-sensitivity, multi-position automatic photochemical steam generating device without memory effect and water vapor interference and a working method thereof.
Background
The hydride generation system is a common sample introduction tool for atomic spectrum detection method due to the realization of effective matrix separation and high sample transmission efficiency, and mainly comprises SnCl2-HCl or NaBH4-an HCl system. However, these systems have some drawbacks: (1) the use of relatively toxic, unstable and expensive reagents is required; (2) a large amount of hydrogen and water vapor can be generated, so that the analyte is greatly diluted, micro plasma used in the atomic spectrum detection process is disturbed and even extinguished, or atomic fluorescence quenching is caused; (3) the detection result is influenced by the interference of transition metal ions.
In order to overcome the above disadvantages, some new vapor generation technologies, such as Photochemical Vapor Generation (PVG), etc., have been developed. The photochemical steam generation system not only can generate a large number of volatile substances, but also has the advantages of high steam generation efficiency, easiness in miniaturization, environmental friendliness, no generation of redundant hydrogen, no interference influence from transition metal ions and the like, and only low-molecular-weight organic acid is used in the photochemical reaction, and organic matters after the photochemical reaction are only degraded into environmentally-friendly carbon dioxide and water, so that the photochemical steam generation system is favored as an attractive green sample introduction technology.
However, the conventional photochemical vapor generation system adopts Flow Injection (FI) to inject sample solution into the reactor one by one for photochemical determination. The flow injection mode generally has the problems of low flux (namely, the flux of a sample is low because of one-by-one sample introduction), low sensitivity, susceptibility to water vapor interference, memory effect (namely, the subsequent detection sensitivity of the sample is low because of the serious water vapor interference and memory effect because of a liquid sample introduction mode), and the like, and a novel photochemical vapor generation system capable of solving the problems is needed to be designed, so that the flux and the sensitivity are remarkably improved, and the memory effect and the interference of water vapor are eliminated as far as possible.
Disclosure of Invention
In order to solve the problems of low flux, low sensitivity, easy water vapor interference and memory effect existing in the prior art, the invention aims to provide a multi-position automatic photochemical steam generating device with high flux, high sensitivity, no memory effect and no water vapor interference and a working method thereof.
The technical scheme adopted by the first aspect of the invention is as follows:
a multi-position automatic photochemical vapor generation device comprises a multi-position photochemical reaction mechanism and an automatic headspace sample injection mechanism;
the multi-position photochemical reaction mechanism comprises an annular ultraviolet lamp, a sample rack, a rotating platform and a plurality of sample bottles, wherein the sample rack and the annular ultraviolet lamp are arranged in a clearance mode, a plurality of reaction stations are arranged on the sample rack at intervals in the annular direction around the annular center of the annular ultraviolet lamp, the rotating platform is used for driving the sample rack to rotate around the annular center of the annular ultraviolet lamp, the sample bottles are quartz headspace bottles and are vertically placed on the reaction stations in a one-to-one correspondence mode;
the automatic headspace sampling mechanism comprises a vertical telescopic frame, a horizontal frame, a purging air inlet pipeline, an air inlet needle tube, an air outlet needle tube and a purging air outlet pipeline, wherein the first end part of the horizontal frame is fixedly connected with the vertical movable part of the vertical telescopic frame, the first end of the purging air inlet pipeline is used for communicating an air path with a carrier gas source, the second end of the purging air inlet pipeline is communicated with the air inlet needle tube, the air path of the air outlet needle tube is communicated with the first end of the purging air outlet pipeline, and the second end of the purging air outlet pipeline is used for communicating the air path with an atomic spectrum excitation source of an atomic spectrum detection instrument;
the second end fixed connection of horizontal bracket the needle that admits air with the needle that gives vent to anger just makes the needle that admits air with the needle that gives vent to anger is vertical respectively downwards, and works as when vertical movable part descends, makes the needle that admits air with the needle that gives vent to anger pierces respectively and is located on the reaction station in the sample bottle, and work as when vertical movable part ascended, make the needle that admits air with the needle that gives vent to anger is followed respectively take out in the sample bottle.
Based on the above invention, a novel photochemical vapor generation device with high flux, high sensitivity, no memory effect and no water vapor interference is provided, namely, on one hand, in a multi-position photochemical reaction mechanism, a plurality of samples can simultaneously generate photochemical vapor reaction under ultraviolet irradiation by designing an ultraviolet lamp into a ring shape, arranging a plurality of sample bottles around the ring-shaped center of the ring-shaped ultraviolet lamp at intervals through a sample frame and rotating the plurality of sample bottles around the ring-shaped center through a rotating platform, thereby greatly improving the flux of the measured samples, on the other hand, in an automatic headspace sampling mechanism, through the configuration of the rotating platform, a vertical expansion bracket, a horizontal bracket, a purging air inlet pipeline, an air inlet needle tube, an air outlet needle tube and a purging air outlet pipeline, the headspace area of a quartz bottle can be communicated with a carrier gas source and an atomic spectrum excitation source one by one, the purpose of adopting gas to sweep and advance a sample to replace traditional flow injection advance a sample is realized, so memory effect and interference of vapor can be eliminated, and the detection sensitivity is greatly improved.
Preferably, the sample holder comprises an inner ring sample holder and an outer ring sample holder, wherein the plurality of reaction stations on the inner ring sample holder are annularly arranged on the inner side of the annular ultraviolet lamp, and the plurality of reaction stations on the outer ring sample holder are annularly arranged on the outer side of the annular ultraviolet lamp.
Preferably, the horizontal frame is a horizontal telescopic frame, wherein the fixed part of the horizontal telescopic frame is used as the first end part of the horizontal frame, and the horizontal movable part of the horizontal telescopic frame is used as the second end part of the horizontal frame.
Preferably, the vertical telescopic frame and the horizontal frame respectively adopt an empty pipe structure, wherein the purging air inlet pipeline and the purging air outlet pipeline are arranged in the empty pipe structure.
Optimally, the height of the needle head of the air inlet needle tube is lower than that of the needle head of the air outlet needle tube.
Preferably, the sample bottle comprises a quartz transparent bottle body and a bottle cap with a polytetrafluoroethylene sealing spacer, wherein the bottle cap is in sealing fit with the transparent bottle body to form a reaction sealing cavity.
Preferably, the system further comprises a pedestal, wherein the annular ultraviolet lamp, the sample rack and the vertical telescopic rack are respectively installed at the top of the pedestal, and the rotating platform is installed inside the pedestal.
The optimized atomic spectrum excitation source device is characterized by further comprising a two-position three-way valve and a carrier gas conduction pipeline, wherein a public air inlet end of the two-position three-way valve is used for communicating a carrier gas source through an air path, a first air outlet end of the two-position three-way valve is communicated with a first end of the purging air inlet pipeline, a second air outlet end of the two-position three-way valve is communicated with a first end of the carrier gas conduction pipeline, and a second end of the carrier gas conduction pipeline is used for communicating an atomic spectrum excitation source of an atomic spectrum detection instrument.
The second aspect of the invention adopts the technical scheme that:
a method of operating a multi-site automatic photo-chemical vapor generation device according to the first aspect, comprising:
after the photochemical reaction is finished, determining a sample bottle to be subjected to sample introduction;
driving the rotary platform to rotate, so that the air inlet needle tube and the air outlet needle tube are respectively aligned to the tops of the sample bottles positioned on the target reaction station;
driving a vertical movable part of the vertical telescopic frame to descend so that an air inlet needle tube and an air outlet needle tube respectively penetrate into sample bottles positioned on a target reaction station;
introducing carrier gas into the sample bottle through the purging gas inlet pipeline and the gas inlet needle tube, and leading out mixed gas of the carrier gas and volatile substances in the bottle from the atomic spectrum excitation source of the atomic spectrum detection instrument through the gas outlet needle tube and the purging gas outlet pipeline;
after the introduction of the carrier gas is stopped, the vertical movable part of the vertical telescopic frame is driven to ascend, so that the gas inlet needle tube and the gas outlet needle tube are respectively drawn out from the sample bottle positioned on the target reaction station.
Optimally, before the photochemical reaction is completed, the working method further comprises:
carrying out aeration treatment on the sample in the sample bottle;
vertically placing a plurality of sample bottles on different reaction stations of a sample rack in a one-to-one correspondence manner;
starting an annular ultraviolet lamp, and irradiating a plurality of sample bottles on a sample rack with ultraviolet rays;
and starting the rotating platform to rotate the sample holder around the annular center of the annular ultraviolet lamp until the photochemical reaction is completed.
The invention has the beneficial effects that:
(1) the invention provides a novel photochemical steam generating device with high flux, high sensitivity, no memory effect and no water vapor interference and a working method thereof, namely, on one hand, in a multi-position photochemical reaction mechanism, a plurality of samples can simultaneously generate photochemical steam reaction under the irradiation of ultraviolet light by designing an ultraviolet lamp into a ring shape, arranging a plurality of sample bottles around the ring-shaped center of the ring-shaped ultraviolet lamp at intervals by a sample frame and rotating the plurality of sample bottles around the ring-shaped center by a rotating platform, thereby greatly improving the flux of the measured samples, on the other hand, in an automatic headspace sampling mechanism, through the configuration of the rotating platform, a vertical expansion bracket, a horizontal bracket, a purging air inlet pipeline, an air inlet needle tube, an air outlet needle tube and a purging air outlet pipeline, the headspace area of a quartz bottle can be communicated with a carrier gas source and an atomic spectrum excitation source one by one, the purpose of adopting gas purging sample injection to replace the traditional flow injection sample injection is realized, so that the memory effect and the interference of water vapor can be eliminated, and the detection sensitivity is greatly improved;
(2) multiposition automatic photochemical vapor generation device has the advantages of convenient use, contribution to improvement of detection accuracy, neat appearance and the like, and is convenient for being combined with miniaturized microplasma atomic emission spectrum to carry out practical application and popularization.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic perspective view of a multi-site automated photochemical vapor generation apparatus provided by the present invention.
FIG. 2 is a schematic view of gas path communication during automatic headspace sampling provided by the present invention.
FIG. 3 is a schematic view of gas path communication before and after automatic headspace sample injection provided by the present invention.
FIG. 4 is a comparison of the emission spectra of mercury atoms provided by the present invention.
FIG. 5 is a comparison graph of the emission spectra of mercury atoms obtained by FI-PVG-PD-OES method and HS-PVG-PD-OES method.
FIG. 6 is a graph comparing results of alternate continuous measurements of low and high concentration standard solutions using FI-PVG-PD-OES and HS-PVG-PD-OES methods provided by the present invention.
FIG. 7 is a comparison graph of a series of calibration curves established by the HS-PVG-PD-OES method and the HS-PVG-AFS method for standard solutions with different Hg (II) concentrations according to the present invention.
FIG. 8 is a statistical chart of the detection results of the HS-PVG-PD-OES method according to the present invention.
In the above drawings, 1-an annular ultraviolet lamp; 12-a sample holder; 121-inner ring sample holder; 122-outer ring sample holder; 14-sample vial; 141-quartz transparent bottle body; 142-a bottle cap; 21-a vertical telescopic frame; 22-horizontal shelf; 23-purging the air inlet line; 24-an inlet needle; 25-air outlet needle tube; 26-purging gas outlet pipeline; 3-a pedestal; 4-two-position three-way valve; 5-the carrier gas conducts the pipeline.
Detailed Description
The invention is further described with reference to the following figures and specific embodiments. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. Specific structural and functional details disclosed herein are merely illustrative of example embodiments of the invention. This invention may, however, be embodied in many alternate forms and should not be construed as limited to the embodiments set forth herein.
It will be understood that, although the terms first, second, etc. may be used herein to describe various elements, these elements should not be limited by these terms. These terms are only used to distinguish one element from another. For example, a first element could be termed a second element, and, similarly, a second element could be termed a first element, without departing from the scope of example embodiments of the present invention.
It should be understood that, for the term "and/or" as may appear herein, it is merely an associative relationship that describes an associated object, meaning that three relationships may exist, e.g., a and/or B may mean: a exists alone, B exists alone, and A and B exist at the same time; for the term "/and" as may appear herein, which describes another associative object relationship, it means that two relationships may exist, e.g., a/and B, may mean: a exists independently, and A and B exist independently; in addition, for the character "/" that may appear herein, it generally means that the former and latter associated objects are in an "or" relationship.
It will be understood that when an element is referred to herein as being "connected," "connected," or "coupled" to another element, it can be directly connected or coupled to the other element or intervening elements may be present. Conversely, if a unit is referred to herein as being "directly connected" or "directly coupled" to another unit, it is intended that no intervening units are present. In addition, other words used to describe the relationship between elements should be interpreted in a similar manner (e.g., "between … …" versus "directly between … …", "adjacent" versus "directly adjacent", etc.).
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments of the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms "comprises," "comprising," "includes" and/or "including," when used herein, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, numbers, steps, operations, elements, components, and/or groups thereof.
It should also be noted that, in some alternative implementations, the functions/acts noted may occur out of the order noted in the figures. For example, two figures shown in succession may, in fact, be executed substantially concurrently, or the figures may sometimes be executed in the reverse order, depending upon the functionality/acts involved.
It should be understood that specific details are provided in the following description to facilitate a thorough understanding of example embodiments. However, it will be understood by those of ordinary skill in the art that the example embodiments may be practiced without these specific details. For example, systems may be shown in block diagrams in order not to obscure the examples in unnecessary detail. In other instances, well-known processes, structures and techniques may be shown without unnecessary detail in order to avoid obscuring example embodiments.
Example one
As shown in fig. 1 to 3, the multi-position automatic photochemical vapor generation device provided by the embodiment includes a multi-position photochemical reaction mechanism and an automatic headspace sampling mechanism; the multi-position photochemical reaction mechanism comprises an annular ultraviolet lamp 11, a sample holder 12, a rotating platform and a plurality of sample bottles 14, wherein the sample holder 12 is arranged with a gap from the annular ultraviolet lamp 11, a plurality of reaction stations are arranged on the sample holder 12 at intervals around the annular center of the annular ultraviolet lamp 11, the rotating platform is used for driving the sample holder 12 to rotate around the annular center of the annular ultraviolet lamp 11, and the sample bottles 14 are quartz headspace bottles and are vertically placed on the reaction stations in a one-to-one correspondence manner; the automatic headspace sampling mechanism comprises a vertical telescopic frame 21, a horizontal frame 22, a purging air inlet pipeline 23, an air inlet needle tube 24, an air outlet needle tube 25 and a purging air outlet pipeline 26, wherein a first end part of the horizontal frame 22 is fixedly connected with a vertical movable part of the vertical telescopic frame 21, a first end of the purging air inlet pipeline 23 is used for being communicated with a carrier gas source through an air path, a second end of the purging air inlet pipeline 23 is communicated with the air inlet needle tube 24 through an air path, the air outlet needle tube 25 is communicated with a first end of the purging air outlet pipeline 26 through an air path, and a second end of the purging air outlet pipeline 26 is used for being communicated with an atomic spectrum excitation source of an atomic spectrum detection; the second end of horizontal shelf 22 is fixed connection the needle tube 24 of admitting air with the needle tube 25 of giving vent to anger just makes the needle head of the needle tube 24 of admitting air with the needle tube 25 of giving vent to anger is vertical downwards respectively, and works as when vertical movable part descends, makes the needle tube 24 of admitting air with the needle tube 25 of giving vent to anger pierces respectively and is located on the reaction station in the sample bottle 14, and when vertical movable part ascends, makes the needle tube 24 of admitting air with the needle tube 25 of giving vent to anger is followed respectively and is taken out in the sample bottle 14.
In the specific structure of the multi-site automatic photochemical vapor generation device, as shown in fig. 1, the multi-site photochemical reaction mechanism is used for simultaneously reacting multiple samples with photochemical vapor under the irradiation of ultraviolet light (generally, all the samples can be reacted within 10 seconds), so that the flux of the samples to be measured is greatly improved. In the multi-position photochemical reaction mechanism, the annular ultraviolet lamp 11 is used for providing ultraviolet light required by photochemical reaction; specifically, the annular ultraviolet lamp 11 can be designed with an inner diameter of 120mm, an outer diameter of 150mm, a power of 20W, and an emission wavelength of 253.7 nm. The sample holder 12 is used for carrying a plurality of sample bottles 14 arranged at intervals in a circumferential direction, so that the sample bottles 14 can be vertically positioned in the inner area and/or the outer area of the annular ultraviolet lamp 11, thereby ensuring that the sample bottles can be irradiated by ultraviolet light to promote photochemical reaction of samples in the bottles; as shown in FIG. 1, the sample holder 12 may be a double plate structure with aligned through holes in the upper and lower plates as reaction stations for vertically positioning the sample bottles 14. The rotating platform (not shown in the drawing) is used for ensuring that ultraviolet light can uniformly irradiate each sample bottle 14 and further sufficiently perform photochemical reaction and ensuring that the top of each sample bottle 14 can be aligned by the air inlet needle tube 24 and the air outlet needle tube 25 one by driving the sample holder 12 to rotate (because the sample holder 12 and the annular ultraviolet lamp 11 are arranged at a gap, and the annular ultraviolet lamp 11 is fixed), so that two needle tubes can be accurately inserted into the bottles to achieve the purpose of headspace sample injection; specifically, the rotary platform can be realized by adopting an existing turntable structure, and the outer diameter can be designed to be 220mm by way of example. The sample bottle 14 is used for providing a photochemical reaction site so as to generate volatile substances for atomic spectrum detection; in particular, the sample bottle 14 may be implemented as a conventional quartz headspace bottle, and the volume may be designed to be 10ml, for example.
The automatic headspace sampling mechanism is used as an automatic sampling system for atomic spectrum detection after photochemical reaction, so that volatile substances in the bottle can be led out to an atomic spectrum excitation source of an atomic spectrum detection instrument, and then the volatile substances can be excited to generate corresponding atomic emission spectral lines, and the purpose of atomic spectrum detection is achieved. In the automatic headspace sampling mechanism, the vertical telescopic frame 21 is used for vertically pressing/lifting the horizontal frame 22, the air inlet needle tube 24 and the air outlet needle tube 25, so that the air inlet needle tube 24 and the air outlet needle tube 25 can respectively penetrate into the sample bottle 14 located on the reaction station when being pressed vertically downwards, and can respectively be drawn out from the sample bottle 14 when being lifted vertically, thereby achieving the purpose of automatic headspace sample bottle. The horizontal shelf 22 is used for carrying the inlet syringe 24 and the outlet syringe 25. The purge inlet line 23 is configured to enable the carrier gas source to be in gas-path communication with the headspace area of the sample bottle 14 when the inlet needle 24 penetrates into the sample bottle 14, so as to introduce a carrier gas (preferably argon Ar) to purge the volatile substances in the sample bottle 14; specifically, the purge inlet line 23 is preferably a corrugated line made of teflon so as to adapt to the expansion and contraction action by using a corrugated structure. The air inlet needle tube 24 is used for puncturing/withdrawing the sample bottle 14; in particular, this can be achieved using conventional syringe syringes. The outlet needle tube 25 is used for puncturing/withdrawing the sample bottle 14; in particular, this can be achieved using conventional syringe syringes. The purging outlet pipeline 26 is used for enabling the atomic spectrum excitation source to be in gas path communication with the inner cavity of the sample bottle 14 when the outlet needle tube 25 penetrates into the sample bottle 14, so that the mixed gas of the carrier gas and volatile substances in the bottle can be led out to the atomic spectrum excitation source; specifically, the purge outlet pipeline 26 is also preferably a corrugated pipeline made of polytetrafluoroethylene material, so as to adapt to the telescopic action by using a corrugated structure.
Therefore, through the detailed structural description of the device, a novel photochemical steam generating device with high flux, high sensitivity, no memory effect and no water vapor interference is provided, namely, on one hand, in a multi-position photochemical reaction mechanism, by designing the ultraviolet lamp into a ring shape, arranging a plurality of sample bottles at intervals around the ring center of the ring ultraviolet lamp by the sample frame, and rotating the plurality of sample bottles around the ring center by the rotating platform, a plurality of samples can simultaneously generate photochemical steam reaction under the ultraviolet irradiation, thereby greatly improving the flux of the measured samples, on the other hand, in an automatic headspace sampling mechanism, through the configuration of the rotating platform, the vertical expansion bracket, the horizontal bracket, the purging air inlet pipeline, the air inlet needle tube, the air outlet needle tube and the purging air outlet pipeline, the headspace area of the quartz bottle can be communicated with the carrier gas source and the atomic spectrum excitation source one by one, the purpose of adopting gas to sweep and advance a sample to replace traditional flow injection advance a sample is realized, so memory effect and interference of vapor can be eliminated, and the detection sensitivity is greatly improved.
The technical effect of the above device is demonstrated below with the detection of mercury.
(1) Since the method is the first attempt to apply the high-flux PVG system and HS (head space) sampling method to the atomic spectrum detection, a miniaturized Point Discharge (PD) atomic emission spectrum is selected as a detector to perform a preliminary experiment on mercury so as to evaluate the feasibility and the practicability of the device, namely, 500 mu g L containing 10% (v/v) formic acid is injected into a quartz sample bottle-1Hg (II) Standard solution 5mL for high throughput PVG; generated Hg0Purging and conveying to a PD atomic spectrum excitation source through Ar carrier gas to perform atomic emission spectrum detection; a comparison of the atomic emission spectra as shown in FIG. 4 was obtained, where typical OH (283, 309nm), NH (337nm) and N were present due to the discharge of Ar2(316, 358 and 380nm), while a clear Hg atomic emission line was observed at 253.65 nm.
(2) To further demonstrate that headspace sampling methods can reduce water vapor interference and increase sensitivity, 5mL of sample containing 10% (v/v) formazan was usedAcid and 500. mu. g L-1The standard solution of Hg (II) compares the results obtained by FI-PVG-PD-OES (Optical emission spectrometer) and HS-PVG-PD-OES; as shown in FIG. 5, compared with the flow injection method, the intensity of the atomic emission lines of OH at 283nm and 309nm obtained by the headspace injection method is significantly reduced by about 3 times, which indicates that the water vapor interference is reduced; whereas the atomic emission line intensity of mercury is stronger at 253.65nm, indicating increased sensitivity.
(3) To verify the absence of memory effect in the device sample injection, a sample containing 1 μ g L was used-1And 500 μ g L-1Different concentrations of Hg standard solution were measured by FI-PVG-PD-OES and HS-PVG-PD-OES in alternating succession as shown in FIG. 6. When injected using the flow injection method, the same was found to be 1 μ g L-1But at 500. mu. g L-1The signal intensity measured after Hg is clearly higher than 500 mu g L-1The strength obtained before Hg, because the adsorptivity of mercury causes severe memory effects in flow injection systems. In contrast, when using headspace gas injection, at 500 μ g L-11 μ g L of Hg measured before and after-1The Hg signal intensity is the same, which shows that HS-PVG-PD-OES has no memory effect, and the method has important significance for measuring the easily adsorbed elements.
(4) Under optimized experimental conditions, a series of calibration curves of standard solutions containing different concentrations of Hg (II) were established using HS-PVG-PD-OES and HS-PVG-AFS (atomic fluorescence Spectroscopy), respectively, as shown in FIG. 7. Linear correlation coefficient (R) of two calibration curves when the injection volume of Hg standard solution is 5mL2) Are all better than 0.99. PD-OES gave a detection limit of 0.02. mu. g L-1AFS of 0.0075 μ g L-1. As shown in FIG. 8, 10 μ g L-1Hg precision by PD-OES (RSD) 2.6%, 0.1 μ g L-1Hg was obtained with a precision (RSD) of 3.8% by AFS. When multiple samples or standard solutions (5mL) were measured using HS-PVG, all samples produced Hg simultaneously0The vapor took only 10 seconds. In addition, the sampling is carried out by directly blowing the headspace gas with Ar, the sampling time required by each sample is about 10 seconds, as shown in figure 8, and the detection time is greatly shortenedIn addition, the analysis flux is improved, and the method is more meaningful for measuring a large number of samples.
The operation method of the multi-position automatic photochemical vapor generation device can include, but is not limited to, the following steps S101 to S109.
S101, carrying out aeration treatment on the sample in the sample bottle 14.
S102, vertically placing a plurality of sample bottles 14 on different reaction stations of the sample rack 12 in a one-to-one correspondence mode.
And S103, starting the annular ultraviolet lamp 11 to irradiate the ultraviolet rays on the plurality of sample bottles 14 on the sample frame 12.
S104, starting the rotating platform to enable the sample holder 12 to rotate around the annular center of the annular ultraviolet lamp 11 until the photochemical reaction is completed.
And S105, after the photochemical reaction is finished, determining a sample bottle 14 to be injected.
And S106, driving the rotating platform to rotate, so that the air inlet needle tube 24 and the air outlet needle tube 25 are respectively aligned to the tops of the sample bottles 14 positioned on the target reaction station.
And S107, driving the vertical movable part of the vertical telescopic frame 21 to descend so that the gas inlet needle tube 24 and the gas outlet needle tube 25 respectively penetrate into the sample bottles 14 positioned on the target reaction station.
And S108, introducing carrier gas into the sample bottle 14 through the purging gas inlet pipeline 23 and the gas inlet needle tube 24, and introducing mixed gas of the carrier gas and volatile substances in the bottle to an atomic spectrum excitation source of an atomic spectrum detection instrument through the gas outlet needle tube 25 and the purging gas outlet pipeline 26.
And S109, after the introduction of the carrier gas is stopped, driving the vertical movable part of the vertical telescopic frame 21 to ascend, and respectively drawing the gas inlet needle tube 24 and the gas outlet needle tube 25 out of the sample bottle 14 positioned on the target reaction station.
Through the steps S101-S104, a plurality of samples can simultaneously generate photochemical steam to react under the irradiation of ultraviolet light (generally, all the photochemical steam can react within 10 seconds), so that the flux of the measured samples is greatly improved; and through the steps S106 to S109, the headspace gas sampling for atomic spectrum detection can be completed for one sample bottle 14. Furthermore, after the step S109 and when determining the next sample bottle 14 to be injected, a round of steps S106 to S109 may be performed for the sample bottle 14 again.
Preferably, the sample holder 12 comprises an inner ring sample holder 121 and an outer ring sample holder 122, wherein the plurality of reaction sites on the inner ring sample holder 121 are arranged on the inner side of the annular ultraviolet lamp 11 in a circumferential direction, and the plurality of reaction sites on the outer ring sample holder 122 are arranged on the outer side of the annular ultraviolet lamp 11 in a circumferential direction. As shown in fig. 1, a plurality of sample bottles 14 can be vertically positioned in the inner and outer regions of the annular ultraviolet lamp 11, thereby maximizing the flux of the measured sample; for example, as shown in fig. 1, five reaction sites may be arranged circumferentially at equal intervals on the inner ring sample holder 121, and fifteen reaction sites may be arranged circumferentially at equal intervals on the outer ring sample holder 122, so that a simultaneous photochemical reaction may be performed on up to twenty samples.
Preferably, the horizontal frame 22 is a horizontal telescopic frame, wherein a fixed portion of the horizontal telescopic frame is used as a first end portion of the horizontal frame 22, and a horizontal movable portion of the horizontal telescopic frame is used as a second end portion of the horizontal frame 22. As shown in FIG. 1, because the sample rack 12 has two layers of inner and outer sample bottles 14, the horizontal expansion rack can drive the air inlet needle tube 24 and the air outlet needle tube 25 to respectively aim at the top of the sample bottle at the inner reaction station or the top of the sample bottle at the outer reaction station, so as to achieve the purpose of respectively injecting headspace gas into the two layers of inner and outer sample bottles 14.
Preferably, the vertical telescopic frame 21 and the horizontal frame 22 respectively adopt an empty pipe structure, wherein the purge air inlet pipeline 23 and the purge air outlet pipeline 26 are arranged inside the empty pipe structure. As shown in FIGS. 2 to 3, the appearance of the whole device is simplified and the device is convenient to use by the design.
Preferably, the height of the needle of inlet needle tube 24 is lower than the height of the needle of outlet needle tube 25. As shown in fig. 2 to 3, by the design, the carrier gas can purge the volatile substances from bottom to top, which is beneficial to forming a purge gas flow, so that the volatile substances are led out along with the carrier gas as much as possible, and the accuracy of atomic spectrum detection is ensured.
Preferably, the sample bottle 14 comprises a quartz transparent bottle body 141 and a bottle cap 142 with a teflon sealing spacer, wherein the bottle cap 142 is in sealing fit with the transparent bottle body 141 to form a reaction sealed cavity. As shown in fig. 1 to 3, a photochemical reaction sealed cavity can be formed by the sealing engagement between the bottle cap 142 and the quartz transparent bottle body 141, so as to ensure that the generated volatile substance does not leak and the external substance does not permeate, thereby ensuring the accuracy of the subsequent atomic spectrum detection. In addition, because the sealing spacer is made of polytetrafluoroethylene materials, the inert characteristic of the sealing spacer can be utilized to prevent the sealing spacer from further carrying out physical or chemical reaction with generated gas, the elastic characteristic of the sealing spacer can be utilized to enable the sealing spacer to be penetrated by the air inlet needle tube 24 and the air outlet needle tube 25 in a sealing way, and after the needle tubes are drawn out, the needle holes can be automatically sealed, so that the sealing characteristic before and after the needle tubes are drawn out is ensured.
Preferably, the system further comprises a pedestal 3, wherein the annular ultraviolet lamp 11, the sample holder 12 and the vertical telescopic frame 21 are respectively installed on the top of the pedestal 3, and the rotating platform is installed inside the pedestal 3. As shown in FIGS. 2 to 3, the appearance of the whole device is simplified and the device is convenient to use by the design. The pedestal 3 may be preferably made of polytetrafluoroethylene.
Optimized, still including two three-way valves 4 and carrier gas conduction pipeline 5, wherein, the public inlet end of two three-way valves 4 is used for gas circuit intercommunication carrier gas source, the first end intercommunication of giving vent to anger of two three-way valves 4 sweep the first end of inlet line 23, the second of two three-way valves 4 is given vent to anger the end intercommunication the first end of carrier gas conduction pipeline 5, the second end that carrier gas conduction pipeline 5 was used for gas circuit intercommunication atomic spectrum excitation source of atomic spectrum detecting instrument. As shown in fig. 2 to 3, the two-position three-way valve 4 is used for realizing gas path switching between purge gas intake and direct gas supply (i.e., a carrier gas source is conducted with a gas path of an atomic spectrum excitation source through the carrier gas conducting pipeline 5), so that in a non-purge sample injection stage (i.e., when a needle tube is not inserted into a sample bottle), the carrier gas can be directly introduced into the atomic spectrum excitation source through the carrier gas conducting pipeline 5, even though the periphery of the atomic spectrum excitation source is always in an argon range, and air is not introduced to interfere with a detection result. Specifically, the two-position three-way valve 4 may specifically employ a solenoid valve of type VK3120, which is a product manufactured by SMC corporation of japan, and is installed inside the pedestal 3. In addition, the carrier gas conducting line 5 is also preferably a corrugated line made of teflon so as to adapt to the expansion and contraction action by using a corrugated structure.
In summary, the multi-position automatic photochemical steam generating device and the working method thereof provided by the embodiment have the following technical effects:
(1) the embodiment provides a novel photochemical steam generating device with high flux, high sensitivity, no memory effect and no water vapor interference and a working method thereof, namely, on one hand, in a multi-position photochemical reaction mechanism, a plurality of sample bottles are annularly arranged around the annular center of an annular ultraviolet lamp at intervals by designing the ultraviolet lamp into an annular shape, and the sample bottles are rotated around the annular center by a rotating platform, so that the samples can simultaneously generate photochemical steam reaction under the irradiation of ultraviolet light, thereby greatly improving the flux of the measured samples, on the other hand, in an automatic headspace sampling mechanism, through the configuration of the rotating platform, a vertical expansion bracket, a horizontal bracket, a purging air inlet pipeline, an air inlet needle tube, an air outlet needle tube and a purging air outlet pipeline, the headspace area of a quartz bottle can be communicated with a carrier gas source and an atomic spectrum excitation source one by one, the purpose of adopting gas purging sample injection to replace the traditional flow injection sample injection is realized, so that the memory effect and the interference of water vapor can be eliminated, and the detection sensitivity is greatly improved;
(2) multiposition automatic photochemical vapor generation device has the advantages of convenient use, contribution to improvement of detection accuracy, neat appearance and the like, and is convenient for being combined with miniaturized microplasma atomic emission spectrum to carry out practical application and popularization.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: modifications of the technical solutions described in the embodiments or equivalent replacements of some technical features may still be made. And such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Finally, it should be noted that the present invention is not limited to the above alternative embodiments, and that various other forms of products can be obtained by anyone in light of the present invention. The above detailed description should not be taken as limiting the scope of the invention, which is defined in the claims, and which the description is intended to be interpreted accordingly.
Claims (10)
1. A multi-position automatic photochemical vapor generation device is characterized in that: comprises a multi-position photochemical reaction mechanism and an automatic headspace sampling mechanism;
the multi-position photochemical reaction mechanism comprises an annular ultraviolet lamp (11), a sample holder (12), a rotating platform and a plurality of sample bottles (14), wherein the sample holder (12) and the annular ultraviolet lamp (11) are arranged at intervals, a plurality of reaction stations are arranged on the sample holder (12) at intervals around the annular center of the annular ultraviolet lamp (11), the rotating platform is used for driving the sample holder (12) to rotate around the annular center of the annular ultraviolet lamp (11), and the sample bottles (14) are quartz headspace bottles and are vertically placed on the reaction stations in a one-to-one correspondence manner;
the automatic headspace sampling mechanism comprises a vertical telescopic frame (21), a horizontal frame (22), a purging air inlet pipeline (23), an air inlet needle tube (24), an air outlet needle tube (25) and a purging air outlet pipeline (26), wherein the first end part of the horizontal frame (22) is fixedly connected with a vertical movable part of the vertical telescopic frame (21), the first end of the purging air inlet pipeline (23) is used for communicating a gas path with a gas carrier source, the second end of the purging air inlet pipeline (23) is communicated with the air inlet needle tube (24), the air outlet needle tube (25) is communicated with the first end of the purging air outlet pipeline (26), and the second end of the purging air outlet pipeline (26) is used for communicating the gas path with an atomic spectrum excitation source of an atomic spectrum detection instrument;
the second end fixed connection of horizontal bracket (22) admit air needle tubing (24) with give vent to anger needle tubing (25) and make admit air needle tubing (24) with the syringe needle of giving vent to anger needle tubing (25) is vertical downwards respectively, and works as when vertical movable part descends, makes admit air needle tubing (24) with it pierces respectively to give vent to anger needle tubing (25) and is located on the reaction station in sample bottle (14), and work as when vertical movable part rose, made admit air needle tubing (24) with it follows respectively to give vent to anger needle tubing (25) take out in sample bottle (14).
2. The multi-site automated photochemical vapor generation apparatus of claim 1, wherein: the sample holder (12) comprises an inner ring sample holder (121) and an outer ring sample holder (122), wherein a plurality of reaction stations on the inner ring sample holder (121) are annularly arranged on the inner side of the annular ultraviolet lamp (11), and a plurality of reaction stations on the outer ring sample holder (122) are annularly arranged on the outer side of the annular ultraviolet lamp (11).
3. The multi-site automatic photochemical vapor generation apparatus of claim 2 wherein: the horizontal frame (22) adopts a horizontal telescopic frame, wherein the fixed part of the horizontal telescopic frame is used as the first end part of the horizontal frame (22), and the horizontal movable part of the horizontal telescopic frame is used as the second end part of the horizontal frame (22).
4. The multi-site automated photochemical vapor generation apparatus of claim 1, wherein: the vertical expansion bracket (21) and the horizontal bracket (22) respectively adopt an empty pipe structure, wherein the purging air inlet pipeline (23) and the purging air outlet pipeline (26) are arranged in the empty pipe structure.
5. The multi-site automated photochemical vapor generation apparatus of claim 1, wherein: the height of the needle head of the air inlet needle tube (24) is lower than that of the needle head of the air outlet needle tube (25).
6. The multi-site automated photochemical vapor generation apparatus of claim 1, wherein: the sample bottle (14) comprises a quartz transparent bottle body (141) and a bottle cap (142) with a polytetrafluoroethylene sealing spacer, wherein the bottle cap (142) is in sealing fit with the transparent bottle body (141) to form a reaction sealed cavity.
7. The multi-site automated photochemical vapor generation apparatus of claim 1, wherein: further comprising a pedestal (3), wherein the annular ultraviolet lamp (11), the sample holder (12) and the vertical telescopic rack (21) are respectively installed on the top of the pedestal (3), and the rotating platform is installed inside the pedestal (3).
8. The multi-site automated photochemical vapor generation apparatus of claim 1, wherein: still lead to pipeline (5) including two three-way valves (4) and carrier gas, wherein, the public inlet end of two three-way valves (4) is used for gas circuit intercommunication carrier gas source, the first end intercommunication of giving vent to anger of two three-way valves (4) sweep the first end of inlet line (23), the second of two three-way valves (4) is given vent to anger the end intercommunication the first end of carrier gas conduction pipeline (5), the second end that carrier gas led to pipeline (5) is used for gas circuit intercommunication atomic spectrum excitation source of atomic spectrum detecting instrument.
9. A method of operating a multi-site automatic photo-chemical vapor generation device according to any one of claims 1 to 8, comprising:
after the photochemical reaction is finished, determining a sample bottle (14) to be injected;
driving the rotary platform to rotate, so that the air inlet needle tube (24) and the air outlet needle tube (25) are respectively aligned to the tops of the sample bottles (14) positioned on the target reaction station;
driving a vertical movable part of a vertical telescopic frame (21) to descend so that an air inlet needle tube (24) and an air outlet needle tube (25) respectively penetrate into a sample bottle (14) positioned on a target reaction station;
introducing carrier gas into the sample bottle (14) through a purging gas inlet pipeline (23) and a gas inlet needle tube (24), and introducing mixed gas of the carrier gas and volatile substances in the bottle to an atomic spectrum excitation source of an atomic spectrum detection instrument through a gas outlet needle tube (25) and a purging gas outlet pipeline (26);
after the introduction of the carrier gas is stopped, the vertical movable part of the vertical telescopic frame (21) is driven to ascend, so that the gas inlet needle tube (24) and the gas outlet needle tube (25) are respectively drawn out from the sample bottle (14) positioned on the target reaction station.
10. A method of operating a multi-site automatic photochemical vapor generation apparatus according to claim 9, further comprising, prior to completion of the photochemical reaction:
carrying out aeration treatment on the sample in the sample bottle (14);
vertically placing a plurality of sample bottles (14) on different reaction stations of a sample rack (12) in a one-to-one correspondence manner;
starting an annular ultraviolet lamp (11) to irradiate a plurality of sample bottles (14) on a sample rack (12) with ultraviolet rays;
and starting the rotating platform to rotate the sample holder (12) around the annular center of the annular ultraviolet lamp (11) until the photochemical reaction is completed.
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