CN112505206B - Absorption constant volume module, ion chromatographic analysis system and analysis method - Google Patents
Absorption constant volume module, ion chromatographic analysis system and analysis method Download PDFInfo
- Publication number
- CN112505206B CN112505206B CN202110139318.8A CN202110139318A CN112505206B CN 112505206 B CN112505206 B CN 112505206B CN 202110139318 A CN202110139318 A CN 202110139318A CN 112505206 B CN112505206 B CN 112505206B
- Authority
- CN
- China
- Prior art keywords
- unit
- sample
- constant volume
- subunit
- detected
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/08—Preparation using an enricher
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Sampling And Sample Adjustment (AREA)
Abstract
The invention provides an absorption constant volume module, an ion chromatographic analysis system and an analysis method, and relates to the technical field of ion chromatographic analysis. The absorption constant volume module is used for an ion chromatographic analysis system and comprises a standard sample unit, a collection unit, a primary constant volume unit, a secondary constant volume unit and a conveying unit; the standard sample unit is used for storing standard samples of ions with different concentrations; the collecting unit is used for collecting a sample to be detected; the primary constant volume unit is connected with the collecting unit; the secondary constant volume unit is respectively connected with the collection unit, the primary constant volume unit and the standard sample unit; the conveying unit is respectively connected with the standard sample unit, the primary constant volume unit and the secondary constant volume unit. Through separately processing the test sample to be detected containing sulfur ions and not containing sulfur ions, after the sulfur ions in the pipeline are washed and absorbed by hydrogen peroxide and then enter the primary constant volume unit for processing, hydrogen peroxide cannot be remained in the secondary constant volume unit, so that the ion chromatographic column cannot be damaged, and the service life of equipment is prolonged.
Description
Technical Field
The invention relates to the technical field of ion chromatographic analysis, in particular to an absorption constant volume module, an ion chromatographic analysis system and an analysis method.
Background
The ion chromatographic analysis system generates various gases after a sample is combusted and pyrolyzed by the high-temperature hydrolysis module, the absorption constant volume module absorbs the various gases generated after pyrolysis to obtain absorption liquid, and the absorption liquid is distributed to the chromatograph for analysis.
In the existing absorption constant volume module, an injection pump is used for controlling the extraction and pushing of absorption liquid obtained by reaction into a quantitative ring for quantification, ions in the absorption liquid in the quantitative ring are enriched on a pre-concentration column, and finally the ions on the pre-concentration column are sent into an ion chromatograph for analysis.
However, the existing absorption constant volume module has the same treatment mode for sulfur-containing absorption liquid and sulfur-free absorption liquid, which causes that after sulfur ions are absorbed by hydrogen peroxide, if hydrogen peroxide in a pipeline is not washed cleanly, residual hydrogen peroxide enters an ion chromatograph, and irreversible damage is caused to an ion chromatographic column.
Disclosure of Invention
For overcoming the not enough among the prior art, the application provides an absorption constant volume module, ion chromatography system and analytical method for solve prior art, after using hydrogen peroxide to absorb the sulphide ion, if hydrogen peroxide in the pipeline washes unclean, remaining hydrogen peroxide gets into ion chromatograph, can cause irreversible damage's technical problem to ion chromatographic column.
In order to achieve the above object, in a first aspect, the present application provides an absorption constant volume module for an ion chromatography system, where the absorption constant volume module includes a standard sample unit, a collection unit, a primary constant volume unit, a secondary constant volume unit, and a delivery unit;
the standard sample unit is used for storing standard samples of ions with different concentrations;
the collecting unit is used for collecting a sample to be detected;
the primary constant volume unit is connected with the collecting unit;
the secondary constant volume unit is respectively connected with the collection unit, the primary constant volume unit and the standard sample unit;
the conveying unit is respectively connected with the standard sample unit, the primary constant volume unit and the secondary constant volume unit;
before the sample to be detected enters an ion chromatograph in the ion chromatographic analysis system for ion chromatographic analysis, the conveying unit is used for pumping the standard sample into the secondary constant volume unit for quantification and conveying the quantified standard sample into the ion chromatograph, and the standard sample is used for calibrating the ion chromatograph and providing reference for the subsequent sample to be detected;
when the collected sample to be detected does not contain sulfur ions, the conveying unit is also used for pumping the sample to be detected into the secondary constant volume unit for quantification and conveying the quantified sample to be detected into the ion chromatograph;
when the collected to-be-detected sample contains sulfur ions, the conveying unit is also used for pumping the to-be-detected sample into the primary constant volume unit for quantification, enrichment and concentration, then the to-be-detected sample enters the secondary constant volume unit for quantification, and then the quantified to-be-detected sample is sent to the ion chromatograph.
In one possible implementation mode, the primary constant volume unit comprises a constant quantum unit and a concentration subunit;
the quantitative quantum unit is used for carrying out first quantification on the sample to be detected containing sulfur ions;
the concentration subunit is connected with the quantification subunit, and the concentration subunit is used for enriching and concentrating the sample to be detected after the first quantification.
In a possible embodiment, the dosing subunit comprises a first dosing ring and a multichannel first switching valve;
two ends of the first quantitative ring are respectively connected with two valve ports of the first switching valve, and the first quantitative ring is used for first quantification of the sample to be detected;
the first switching valve is connected with the collecting unit and the concentrating subunit respectively, and the first switching valve is used for realizing that the first quantitative ring is selectively communicated with the collecting unit or the concentrating subunit.
In one possible embodiment, the concentration subunit comprises a pre-concentration column and a multi-channel second switching valve;
two ends of the pre-concentration column are respectively connected with two valve ports of the second switching valve, and the pre-concentration column is used for enriching and concentrating the sample to be tested after first quantification;
the second switching valve is respectively connected with the quantitative subunit and the secondary constant volume unit, and the second switching valve is used for selectively communicating the pre-concentration column with the quantitative subunit or the secondary constant volume unit.
In a possible implementation mode, the primary constant volume unit further comprises a collection container, an inlet of the collection container is connected with the concentration subunit, an outlet of the collection container is connected with the secondary constant volume unit, and the collection container is used for collecting the concentrated sample to be tested.
In one possible embodiment, the primary constant volume unit comprises a first flushing subunit and a second flushing subunit;
the first washing subunit is used for washing the quantitative subunit, the first washing subunit comprises a first cleaning solution container and a first pump, and the first cleaning solution container, the first pump and the quantitative subunit are sequentially connected;
the second washing subunit is used for washing the concentration subunit, the second washing subunit comprises a second cleaning solution container and a second pump, and the second cleaning solution container, the second pump and the concentration subunit are sequentially connected.
In one possible embodiment, the secondary constant volume unit comprises a second quantitative ring and a multi-channel third switching valve;
two ends of the second quantitative ring are respectively connected with two valve ports of the third switching valve;
the third switching valve is respectively connected with the standard sample unit, the collection unit, the primary constant volume unit, the conveying unit and the ion chromatograph, and the third switching valve is used for realizing that the second quantitative ring is selectively communicated with the standard sample unit, the collection unit, the primary constant volume unit, the conveying unit or the ion chromatograph.
In a second aspect, the present application further provides an ion chromatography system, comprising an automatic sample introduction module, a high temperature hydrolysis module, an ion chromatograph, and the absorption constant volume module;
the automatic sample feeding module is used for automatically feeding a sample to the high-temperature hydrolysis module;
the high-temperature hydrolysis module, the absorption constant volume module and the ion chromatograph are sequentially connected.
In a possible embodiment, the pyrohydrolysis module comprises a combustion furnace, the combustion furnace comprises a housing and a combustion pipe, the combustion pipe is arranged in the housing, and four sets of cooling fans are arranged on a rear cover of the housing.
In a third aspect, the present application further provides an ion chromatography method using the ion chromatography system provided above, where the ion chromatography method includes:
conveying a sample;
carrying out high-temperature hydrolysis on the sample;
condensing and collecting a gaseous sample generated after hydrolysis to obtain a sample to be detected;
calibrating an ion chromatograph through a standard sample;
and quantifying the sample to be detected, and carrying out ion chromatography analysis on the quantified sample to be detected.
Compared with the prior art, the beneficial effects of the application are that:
compared with the prior art, the absorption constant volume module, the ion chromatographic analysis system and the analysis method provided by the application are characterized in that the absorption constant volume module is used for the ion chromatographic analysis system and comprises a standard sample unit, a collection unit, a primary constant volume unit, a secondary constant volume unit and a conveying unit; the standard sample unit is used for storing standard samples of ions with different concentrations; the collecting unit is used for collecting a sample to be detected; the primary constant volume unit is connected with the collecting unit; the secondary constant volume unit is respectively connected with the collection unit, the primary constant volume unit and the standard sample unit; the conveying unit is respectively connected with the standard sample unit, the primary constant volume unit and the secondary constant volume unit.
According to the absorption constant volume module, before a sample to be detected enters an ion chromatograph in an ion chromatographic analysis system for ion chromatographic analysis, a conveying unit is used for pumping a standard sample into a secondary constant volume unit for quantification, the quantified standard sample is sent into the ion chromatograph, the ion chromatograph is calibrated through the standard sample, the precision of the ion chromatograph is determined, and meanwhile, a reference is provided for a subsequent sample to be detected; when the collected sample to be tested does not contain sulfur ions, the conveying unit is also used for pumping the sample to be tested into the secondary constant volume unit for quantification, and the quantified sample to be tested is sent into the ion chromatograph through the conveying unit; when the collected to-be-detected sample contains sulfur ions, the conveying unit is also used for pumping the to-be-detected sample into the primary constant volume unit for quantification, enrichment and concentration, then the to-be-detected sample enters the secondary constant volume unit for quantification, and then the to-be-detected sample quantified by the secondary constant volume unit is sent into the ion chromatograph through the conveying unit. The application provides an absorption constant volume module, the sample that awaits measuring that will contain the sulphur ion and do not contain the sulphur ion is separately handled, therefore, to the sample that awaits measuring that contains the sulphur ion, wash with hydrogen peroxide solution and get into one-level constant volume unit after absorbing and carry out the ration, enrichment and concentrated processing back, basically having decomposed hydrogen peroxide solution, no hydrogen peroxide solution has been gone into during reentrant second grade constant volume unit, so when handling the sample that awaits measuring that does not contain the sulphur ion again, can not remain hydrogen peroxide solution in the second grade constant volume unit, can not damage the ion chromatographic column, extension equipment life.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 illustrates a block schematic diagram of an ion chromatography system provided by an embodiment of the present application;
FIG. 2 is a schematic block diagram illustrating an absorption volumetric module provided by an embodiment of the present application;
fig. 3 is a schematic module diagram illustrating a primary constant volume unit in an absorption constant volume module provided in an embodiment of the present application;
FIG. 4 is a schematic block diagram illustrating a collection unit in an absorption volumetric module provided by an embodiment of the present application;
FIG. 5 is a schematic diagram of an ion chromatography system according to an embodiment of the present disclosure;
fig. 6 is a flow chart illustrating steps of an ion chromatography method provided in an embodiment of the present application.
Description of the main element symbols:
100-an automatic sample introduction module;
200-high temperature hydrolysis module; 210-a combustion furnace; 211-a housing; 212-a combustion tube;
300-absorption constant volume module; 310-standard sample cell; 311-standard sample vial; 312-a fourth switching valve; 320-a collection unit; 321-a water supply subunit; 3210-water storage bottle; 3211-a fourth pump; 322-a condensate collector subunit; 3220-condenser; 3221-a collection bottle; 323-third rinse subunit; 3230-third cleaning solution container; 3231-fifth pump; 3232-sixth pump; 330-primary constant volume unit; 331-a quantifying subunit; 3310-first amount of ring; 3311-first switching valve; 332-a first rinse subunit; 3320-first cleaning solution container; 3321-first pump; 333-a second flushing subunit; 3330-a second cleaning solution container; 3331-a second pump; 334-a concentration subunit; 3340-pre-concentration column; 3341-second switching valve; 335-a collection container; 340-a secondary constant volume unit; 341-second quantification ring; 342-a third switching valve; 350-a conveying unit; 351-a third pump; 352-a liquid storage pipe; 360-a waste liquid collection unit; 361-waste liquid bottle; 362-seventh pump;
400-ion chromatography;
500-atmosphere protection module.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.
In the description of the present invention, it is to be understood that the terms "central," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," "circumferential," and the like are used in the orientations and positional relationships indicated in the drawings for convenience in describing the invention and to simplify the description, and are not intended to indicate or imply that the referenced device or element must have a particular orientation, be constructed and operated in a particular orientation, and are not to be considered limiting of the invention.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
In the present invention, unless otherwise expressly stated or limited, the terms "mounted," "connected," "secured," and the like are to be construed broadly and can, for example, be fixedly connected, detachably connected, or integrally formed; can be mechanically or electrically connected; either directly or indirectly through intervening media, either internally or in any other relationship. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
In the present invention, unless otherwise expressly stated or limited, the first feature "on" or "under" the second feature may be directly contacting the first and second features or indirectly contacting the first and second features through an intermediate. Also, a first feature "on," "over," and "above" a second feature may be directly or diagonally above the second feature, or may simply indicate that the first feature is at a higher level than the second feature. A first feature being "under," "below," and "beneath" a second feature may be directly under or obliquely under the first feature, or may simply mean that the first feature is at a lesser elevation than the second feature.
Example one
Referring to fig. 1, the present embodiment provides an ion chromatography system for performing chromatography on various ions in a sample to be detected to obtain a ratio of the ions in the sample to be detected.
The ion chromatography system provided by the embodiment comprises an automatic sample introduction module 100, a high-temperature hydrolysis module 200, an ion chromatograph 400 and an absorption constant volume module 300, wherein the high-temperature hydrolysis module 200, the absorption constant volume module 300 and the ion chromatograph 400 are sequentially connected.
The automatic sample feeding module 100 is used for automatically feeding a sample to the high-temperature hydrolysis module 200; the high-temperature hydrolysis module 200 is used for performing high-temperature hydrolysis on the fed sample to obtain a gaseous sample after hydrolysis; the absorption constant volume module 300 is used for condensing the gaseous sample into a liquid sample to be measured, and collecting and quantifying the sample; the ion chromatograph 400 is used for performing ion chromatography analysis on a quantitative sample to be measured and a standard sample.
Above-mentioned, autoinjection module 100 includes triaxial manipulator, quartz boat and sample tray, is provided with on the sample tray and has loaded the sample that awaits the use, and in triaxial manipulator snatched the quartz boat and sent into pyrohydrolysis module 200, pyrohydrolysis module 200 carried out pyrohydrolysis to the sample to obtain the sample that awaits measuring, wherein, the quartz boat can load solid-state or liquid sample.
The autoinjection module 100 realizes that the sample is pushed into the high temperature hydrolysis module 200 automatically, and can be pushed to the position in the high temperature hydrolysis module 200 through program control, so as to control the sample to carry out high temperature hydrolysis in different temperature areas of the high temperature hydrolysis module 200 according to the combustion characteristics of different samples.
Referring to fig. 1 and 5, the pyrohydrolysis module 200 includes a burner 210, wherein the burner 210 is used for heating the sample advanced by the autosampler module 100.
The combustion furnace 210 includes a housing 211 and a combustion tube 212, the combustion tube 212 is disposed in the housing 211, the combustion tube 212 heats the sample, a rear cover of the housing 211 is provided with four sets of heat dissipation fans (not shown) for dissipating heat generated by high temperature combustion to the outside in time, and the heating temperature of the combustion furnace 210 can reach 1200 ℃.
Referring to fig. 2, the absorption constant volume module 300 includes a standard sample unit 310, a collection unit 320, a primary constant volume unit 330, a secondary constant volume unit 340, and a delivery unit 350. The standard sample unit 310 is used for storing standard samples of ions with different concentrations; the collecting unit 320 is connected to the combustion furnace 210, and the collecting unit 320 is used for collecting the sample to be tested generated by the high-temperature hydrolysis of the combustion furnace 210. The primary constant volume unit 330 is connected with the collection unit 320; the secondary constant volume unit 340 is respectively connected with the collection unit 320, the primary constant volume unit 330 and the standard sample unit 310; the delivery unit 350 is respectively connected with the standard sample unit 310, the primary constant volume unit 330 and the secondary constant volume unit 340.
Before the sample to be tested enters the ion chromatograph 400 for ion chromatography analysis, the conveying unit 350 pumps the standard sample into the secondary constant volume unit 340 for quantification, the quantified standard sample is sent into the ion chromatograph 400 by the conveying unit 350 for ion chromatography analysis, and then the sample to be tested is subjected to ion chromatography analysis. It will be appreciated that the ion chromatograph 400 is calibrated with standard samples to determine the accuracy of the ion chromatograph 400 while providing a reference for subsequent samples to be tested.
In this embodiment, when the sample to be measured needs to be subjected to ion chromatography, the following two cases are distinguished:
in the first case, when the collected sample to be tested does not contain sulfur ions, the conveying unit 350 pumps the sample to be tested into the secondary constant volume unit 340 for quantification, and the quantified sample to be tested is sent to the ion chromatograph 400 for analysis by the conveying unit 350.
In the second case: when the collected to-be-detected sample contains sulfur ions, the conveying unit 350 pumps the to-be-detected sample into the primary constant volume unit 330 for quantification, enrichment and concentration, the to-be-detected sample enters the secondary constant volume unit 340 for quantification, and the quantified to-be-detected sample is sent to the ion chromatograph 400 for analysis through the conveying unit 350.
Therefore, in the ion chromatography system provided by this embodiment, the to-be-detected sample containing sulfur ions and not containing sulfur ions is separately processed in the absorption constant volume module 300, and therefore, for the to-be-detected sample containing sulfur ions, the sulfur ions in the pipeline are washed and absorbed by hydrogen peroxide and then enter the primary constant volume unit 330 for quantification, enrichment and concentration, hydrogen peroxide is decomposed basically, and no hydrogen peroxide exists when the to-be-detected sample containing no sulfur ions is re-processed, so that hydrogen peroxide does not remain in the secondary constant volume unit 340, and therefore, the ion chromatography column is not damaged, and the service life of the device is prolonged.
Example two
Referring to fig. 1 to 6, the present embodiment provides an ion chromatography system for performing chromatography on various ions in a sample to be detected to obtain a ratio of the ions in the sample to be detected. The present embodiment is an improvement on the first embodiment, and compared with the first embodiment, the difference is that:
referring to fig. 1, fig. 2 and fig. 5, in the present embodiment, the absorption constant volume module 300 includes a standard sample unit 310, a collection unit 320, a primary constant volume unit 330, a secondary constant volume unit 340 and a delivery unit 350.
The standard sample unit 310 includes a plurality of standard sample vials 311 and a multi-channel fourth switching valve 312, wherein each standard sample vial 311 is used for storing an ion solution with one concentration, that is, a standard sample, and the concentration of the standard sample stored in each standard sample vial 311 is different. The plurality of standard sample bottles 311 are connected to a valve port of the fourth switching valve 312 via a pipe line.
In the present embodiment, five or six standard sample vials 311 are used to load standard samples, and it should be understood that the above description is only illustrative and should not be taken as a limitation on the scope of the present application.
Hereinafter, five standard sample bottles 311 are taken as an example, wherein the five standard sample bottles 311 are loaded with standard samples, respectively, and the ion concentrations of the standard samples in the five standard sample bottles 311 are sequentially increased. It will be appreciated that the minimum and maximum ion concentrations of the standard sample should encompass the range of ion concentrations of the sample to be measured in order to provide an accurate reference for the sample to be measured.
In the present embodiment, the multichannel fourth switching valve 312 is a ten-way valve, and thus the fourth switching valve 312 includes ten inlet ports a1 to a10 and one outlet port a0, and five standard sample bottles 311 are respectively connected to the five inlet ports a1 to a5 of the ten-way valve through pipelines.
Referring to fig. 2, fig. 3 and fig. 5, the primary constant volume unit 330 includes a constant volume subunit 331, a concentration subunit 334, a first rinsing subunit 332 and a second rinsing subunit 333. The quantitative quantum unit 331 is used for carrying out first quantification on a sample to be detected containing sulfur ions; the concentration subunit 334 is connected to the quantifying subunit 331, and the concentration subunit 334 is configured to enrich and concentrate the first quantified sample to be tested; the first washing subunit 332 is connected to the quantifying subunit 331, the first washing subunit 332 is configured to wash the quantifying subunit 331, and the first washing subunit 332 can also send the first quantitative sample to be tested from the quantifying subunit 331 to the concentrating subunit 334; the second washing subunit 333 is connected to the concentration subunit 334, the second washing subunit 333 is used for washing the concentration subunit 334, and the second washing subunit 333 can also send out the sample to be tested, which is enriched and concentrated in the concentration subunit 334.
It will be appreciated that the purpose of the enrichment concentration of the concentration subunit 334 is to: the method is used for enriching anions in the first quantitative sample to be tested, such as sulfur ions in the sample to be tested, and can also be used for concentrating the first quantitative sample to be tested.
Referring to fig. 3 and 5, the quantitative subunit 331 further includes a first quantitative ring 3310 and a multi-channel first switching valve 3311, two ends of the first quantitative ring 3310 are respectively connected to two valve ports of the first switching valve 3311, and the first quantitative ring 3310 is used for first quantitative determination of the sample to be measured; the first switching valve 3311 is connected to the collecting unit 320 and the concentrating sub-unit 334, respectively, and the first switching valve 3311 is used to enable the first metering ring 3310 to selectively communicate with the collecting unit 320 or the concentrating sub-unit 334.
Specifically, in the present embodiment, the multi-path first switching valve 3311 is selected to be a six-way valve, and thus, the first switching valve 3311 includes six ports B1 to B6, in which the ports B2 and B5 of the first switching valve 3311 are respectively communicated with both ends of the first metering ring 3310 through pipes; the port B6 of the first switching valve 3311 is connected to the port a0 of the fourth switching valve 312 by a pipe.
The first rinse subunit 332 includes a first cleaning solution container 3320 and a first pump 3321. The first cleaning solution container 3320, the first pump 3321, and the dosing subunit 331 are connected in sequence. Specifically, a liquid inlet of the first pump 3321 is connected to the first cleaning liquid container 3320 through a pipeline, and a liquid outlet of the first pump 3321 is connected to the port B4 of the first switching valve 3311 through a pipeline.
In some embodiments, the cleaning liquid stored in the first cleaning liquid container 3320 is Ultrapure water, wherein Ultrapure water (ultra water), which is also referred to as UP water, refers to water having a resistivity of 18M Ω · M (25 ℃). This water removes almost all atoms of water except oxygen and hydrogen. May be used to remove ions from the dosing subunit 331. In this embodiment, the first pump 3321 pumps the ultra-pure water to flush the residual liquid in the first quantitative ring 3310, which can be used to remove the ions in the first quantitative ring 3310, thereby achieving the purpose of cleaning the first quantitative ring 3310.
In other embodiments, the first pump 3321 may be a peristaltic pump or a syringe pump, and in this embodiment, the peristaltic pump is selected so that the cleaning solution can be isolated in the pump tube, thereby preventing the cleaning solution in the tube from being contaminated and improving the analysis accuracy.
Further, the concentration subunit 334 includes a pre-concentration column 3340 and a multi-channel second switching valve 3341, two ends of the pre-concentration column 3340 are respectively connected to two valve ports of the second switching valve 3341, and the pre-concentration column 3340 is used for enriching and concentrating the sample to be measured after the first quantification; the second switching valve 3341 is respectively connected to the quantitative subunit 331 and the secondary constant volume unit 340, and the second switching valve 3341 is configured to selectively communicate the pre-concentration column 3340 with the quantitative subunit 331 or the secondary constant volume unit 340.
Specifically, in the present embodiment, the multi-channel second switching valve 3341 is selected to be a six-way valve, and thus, the second switching valve 3341 includes six ports C1 to C6, wherein the ports C2 and C5 of the second switching valve 3341 are respectively communicated with both ends of the preconcentration column 3340 through pipelines; the C6 port of the second switching valve 3341 is connected to the B3 port of the first switching valve 3311 via a pipe to allow the sample to be tested, which has been quantified for the first time in the first quantification ring 3310, to enter the pre-concentration column 3340.
The second rinse subunit 333 includes a second cleaning solution container 3330 and a second pump 3331, and the second cleaning solution container 3330, the second pump 3331, and the concentration subunit 334 are connected in this order. Specifically, a liquid inlet of the second pump 3331 is connected to the second cleaning liquid container 3330 through a pipeline, and a liquid outlet of the second pump 3331 is connected to a C3 valve port of the second switching valve 3341 through a pipeline.
In some embodiments, the cleaning fluid stored in the second cleaning fluid container 3330 is an eluent, which is also referred to as an eluant, and the second pump 3331 pumps the eluent into the line to back flush the ions attached to the pre-concentration column 3340.
In other embodiments, the second pump 3331 may be a syringe pump, and the cleaning solution stored in the second cleaning solution container 3330 is pumped by the syringe pump. Of course, the second pump 3331 may be a plunger pump, a ceramic pump, or the like.
Further, in this embodiment, the primary constant volume unit 330 further includes a collection container 335, an inlet of the collection container 335 is connected to the concentration subunit 334, an outlet of the collection container 335 is connected to the secondary constant volume unit 340, and the collection container 335 is configured to collect the concentrated sample to be tested. Specifically, the inlet of the collection container 335 is connected to the C4 port of the second switching valve 3341 through a pipeline, and the outlet of the collection container 335 is connected to the a9 port of the fourth switching valve 312 through a pipeline, and indirectly connected to the secondary constant volume unit 340.
Referring to fig. 2, fig. 3 and fig. 5, it can be understood that the ions on the pre-concentration column 3340 are unevenly distributed, and the ions on the pre-concentration column 3340 are directly eluted into the ion chromatograph 400, which may cause an inaccurate analysis result. In this embodiment, the second pump 3331 is used to pump the eluent to back-flush the anions attached to the preconcentration column 3340, and the rinsed anions are sent to the collection container 335 to be collected, so that the rinsed anions are uniformly dispersed in the collection container 335, the sample to be measured with uniformly dispersed anions is sent to the secondary constant volume unit 340 through the conveying unit 350 to be quantified for the second time, and finally the sample to be measured after being quantified for the second time is sent to the ion chromatograph 400 by the conveying unit 350 to be subjected to ion chromatography, thereby improving the analysis result.
Referring to fig. 2, fig. 3 and fig. 5, the secondary constant volume unit 340 includes a second quantitative ring 341 and a multi-channel third switching valve 342, two ends of the second quantitative ring 341 are respectively connected to two valve ports of the third switching valve 342, the second quantitative ring 341 is configured to quantify a sample entering the secondary constant volume unit 340, where the sample may include a standard sample, a sample to be measured in the collection unit 320, and a sample to be measured processed by the primary constant volume unit 330; the third switching valve 342 is connected to the standard sample unit 310, the collection unit 320, the primary constant volume unit 330, the transfer unit 350, and the ion chromatograph 400, respectively. The third switching valve 342 is configured to selectively communicate the second quantitative ring 341 with the standard sample unit 310, the collection unit 320, the primary constant volume unit 330, the delivery unit 350, or the ion chromatograph 400.
In the present embodiment, the multi-channel third switching valve 342 also selects a six-way valve, so that the third switching valve 342 includes six ports D1 to D6, wherein the ports D2 and D5 of the third switching valve 342 are respectively communicated with two ends of the second dosing ring 341 through pipelines; the port D6 of the third switching valve 342 is connected to the port B1 of the first switching valve 3311 by a line. For introducing the labeled sample and the sample to be measured into the second quantitative ring 341 by switching the first switching valve 3311.
Further, the ports D3 and D4 of the third switching valve 342 are connected to the inlet and outlet of the ion chromatograph 400 via pipes, respectively, for introducing the sample in the second quantitative ring 341 into the ion chromatograph 400.
The conveying unit 350 includes a third pump 351 and a liquid storage pipe 352, a liquid inlet end of the third pump 351 is connected to the first cleaning liquid container 3320 through a pipeline, a liquid outlet end of the third pump 351 is connected to the liquid storage pipe 352 through a pipeline, and another port of the liquid storage pipe 352 is connected to a valve port D1 of the third switching valve 342 through a pipeline.
The liquid storage tube 352 can store liquid in the pipeline to ensure that other liquid in the liquid storage tube 352 does not enter the first cleaning liquid container 3320 when the third pump 351 is switched to the positive rotation and the negative rotation, so as to prevent the cleaning liquid in the first cleaning liquid container 3320 from being polluted.
Referring to fig. 2, 4 and 5, the collecting unit 320 includes a water supply subunit 321, a condensation collecting subunit 322 and a third flushing subunit 323.
Specifically, the water supply subunit 321 includes a water storage bottle 3210 and a fourth pump 3211, ultrapure water is stored in the water storage bottle 3210, a liquid inlet end of the fourth pump 3211 is connected to the water storage bottle 3210 through a pipeline, a liquid outlet end of the fourth pump 3211 is connected to an inlet end of the combustion pipe 212 through a pipeline, and the fourth pump 3211 is configured to pump ultrapure water into the combustion pipe 212, so that the sample is hydrolyzed at a high temperature in the combustion pipe 212, thereby obtaining a gaseous sample. In this embodiment, the fourth pump 3211 selects a syringe pump, and injects ultrapure water into the combustion pipe 212 by utilizing the characteristic of the syringe pump that has a high discharge pressure.
The condensation collection subunit 322 includes a condenser 3220, a cold water circulation device (not shown), and a collection bottle 3221, wherein the condenser 3220 is connected to an outlet end of the combustion tube 212, and is configured to condense a gaseous sample generated during high-temperature hydrolysis in the combustion furnace 210 into a liquid sample to be measured, the cold water circulation device is configured to provide cooling water for the condenser 3220, and the collection bottle 3221 is configured to collect the sample to be measured.
The condenser 3220 includes an outer tube (not shown) and an inner tube (not shown), the outer tube is sleeved on the inner tube, the inner tube penetrates through the outer tube, the inner tube is coiled into a serpentine shape, an inlet of the inner tube is connected to an outlet of the combustion tube 212, and an outlet of the inner tube is connected to a liquid inlet of the collecting bottle 3221.
It can be understood that the sample is hydrolyzed by high temperature combustion in the combustion tube 212 and then discharged from the outlet of the combustion tube 212 into the inner tube in a gaseous state, and the cold water circulating device introduces circulating cooling water between the outer tube and the inner tube to condense the high temperature gaseous sample entering the inner tube into the low temperature liquid sample to be tested. And the inner pipe of the serpentine structure can better condense the gas state into the liquid state, and the condensation effect is good.
The collection bottle 3221 has a certain volume and can accommodate a sample to be measured, and a liquid outlet of the collection bottle 3221 is connected to the valve port a10 of the fourth switching valve 312 through a pipeline, so as to introduce the sample to be measured into the absorption constant volume module 300.
And the third washing subunit 323 comprises a third washing liquid container 3230 and a fifth pump 3231, wherein a liquid inlet of the fifth pump 3231 is connected with the third washing container through a pipeline, and a liquid outlet of the fifth pump 3231 is connected with an outlet end of the combustion pipe 212 through a pipeline. Hydrogen peroxide is stored in the third cleaning solution container 3230. In some embodiments, the fifth pump 3231 may also be an injection pump, and the fifth pump 3231 pumps hydrogen peroxide into the pipeline, and the hydrogen peroxide absorbs sulfur ions remaining in the pipeline connected between the combustion pipe 212 and the collection bottle 3221 to generate sulfides.
Further, in order to avoid hydrogen peroxide remaining in the pipeline, the water storage bottle 3210 in the water supply subunit 321 is connected to the outlet end of the combustion pipe 212 through a sixth pump 3232, the sixth pump 3232 selects a peristaltic pump, and the sixth pump 3232 extracts ultrapure water to clean the hydrogen peroxide remaining in the connecting pipeline between the combustion pipe 212 and the collecting bottle 3221, so that hydrogen peroxide is prevented from entering the secondary constant volume unit 340, and further, the chromatographic column is prevented from being damaged.
Further, in order to avoid the hydrogen peroxide remaining in the pipeline, the other outlet of the water storage bottle 3210 of the water supply subunit 321 is connected to the port a7 of the fourth switching valve 312 through a pipeline, so as to clean the pipeline between the fourth switching valve 312 and the first switching valve 3311 and the collecting bottle 3221, respectively, and avoid the hydrogen peroxide remaining on the pipeline, thereby avoiding the damage to the chromatographic column.
Referring to fig. 1 and 5, in the present embodiment, the absorption constant volume module 300 further includes a waste liquid collecting unit 360, the waste liquid collecting unit 360 includes a waste liquid bottle 361, and an inlet end of the waste liquid bottle 361 is respectively connected to the C1 valve port of the second switching valve 3341 and the a8 valve port of the fourth switching valve 312 through a pipeline for collecting waste liquid generated after the pipeline is cleaned.
Further, the inlet end of the waste liquid bottle 361 is connected to the liquid outlet of the collection bottle 3221 through a seventh pump 362, and the seventh pump 362 may also be a peristaltic pump for collecting liquid in the large collection bottle 3221, such as a sample to be tested, waste liquid after washing, and the like.
The ion chromatography system provided in this embodiment further includes an atmosphere protection module 500, where the atmosphere protection module 500 is connected to the inlet end of the combustion tube 212, and is used to provide atmosphere protection for the sample in the combustion tube 212 during the high-temperature hydrolysis. The gas provided by the atmosphere protection module 500 is an inert gas, such as argon, and may be nitrogen.
Referring to fig. 5 and fig. 6, the present embodiment also provides an ion chromatography method using the ion chromatography system of the present embodiment, wherein the ion chromatography method includes the following steps:
s100: conveying a sample;
specifically, the three-axis manipulator grabs a quartz boat and sends the quartz boat into the combustion tube 212, and the quartz boat is loaded with a sample to be used.
S200: carrying out high-temperature hydrolysis on the sample;
specifically, the combustion furnace 210 heats the combustion tube 212 to a temperature of 1200 ℃, and the fourth pump 3211 pumps ultrapure water into the combustion tube 212 to hydrolyze the sample at high temperature in the combustion tube 212. The atmosphere protection module 500 introduces argon gas into the combustion tube 212 for atmosphere protection.
S300: condensing and collecting a gaseous sample generated after hydrolysis to obtain a sample to be detected;
specifically, the sample generates a gaseous sample after high-temperature hydrolysis, the gaseous sample is cooled into a liquid sample to be detected by the condenser 3220, and the sample to be detected is collected by the collecting bottle 3221.
S400: calibrating the ion chromatograph 400 by a standard sample;
it will be appreciated that in performing ion chromatography on a sample to be tested, calibration of the ion chromatograph 400 is required to determine the accuracy of the ion chromatograph 400, while providing a reference for ion chromatography of the sample to be tested.
The method comprises the following specific steps:
s410: the fourth switching valve 312 is started, so that the ports A1 to A5 of the fourth switching valve 312, which are connected with the standard sample, are sequentially communicated with the port A0, and the standard sample enters the first switching valve 3311 from the port A0; meanwhile, the first switching valve 3311 is switched to communicate with the port B6 and the port B1; the third switching valve 342 is switched to communicate with the port D5 at D6 and with the port D1 at D2. In the delivery unit 350, the third pump 351 draws the standard sample into the second quantitative ring 341 for quantitative determination;
s411: after the standard sample is quantified once in the second quantitative ring 341, the third switching valve 342 is switched to D4 to communicate with the D5 valve port, and D2 to communicate with the D1 valve port; at the same time, the third pump 351 is activated to send the standard sample in the second quantitative ring 341 to the ion chromatograph 400 for analysis.
S500: and quantifying the sample to be detected, and carrying out ion chromatography analysis on the quantified sample to be detected.
The quantitative mode for the to-be-detected sample containing no sulfur ions and sulfur ions is different, and the method specifically comprises the following steps:
the quantitative step for the sulfur ion-free sample to be tested comprises the following steps:
s510: the fourth switching valve 312 is actuated, so that the fourth switching valve 312 is switched to communicate with the port A10 and the port A0, and simultaneously, the first switching valve 3311 is switched to communicate with the port B6 and the port B1; the third switching valve 342 is switched to communicate with the port D5 at D6 and with the port D1 at D2. In the conveying unit 350, the third pump 351 extracts the sulfur-free sample to be measured in the collection bottle 3221 and directly enters the second quantitative ring 341 for quantitative determination;
s511: after the sample to be tested is quantified once in the second quantifying ring 341, the third switching valve 342 is switched to D4 to be communicated with the D5 valve port, and D2 is communicated with the D1 valve port; the third pump 351 is reversed to send the sample to be measured in the second quantitative ring 341 to the ion chromatograph 400 for analysis.
The quantitative step aiming at the sample to be tested containing the sulfur ions comprises the following steps:
s520: the fourth switching valve 312 is started, so that the fourth switching valve 312 is switched to communicate with the port A10 and the port A0, meanwhile, the first switching valve 3311 is switched to communicate with the port B6 and the port B5, and the port B1 and the port B2; the third switching valve 342 is switched to communicate with port D6 and port D1. In the conveying unit 350, the third pump 351 extracts the sulfur-containing sample to be measured in the collection bottle 3221 and directly enters the first quantitative ring 3310 for quantitative determination;
s521: after the sample to be measured is quantified for the first time in the first quantitative ring 3310, the first switching valve 3311 is switched to the B4 to communicate with the B5 valve port, the B2 to communicate with the B3 valve port, meanwhile, the second switching valve 3341 is switched to the C6 to communicate with the C5 valve port, the C2 to communicate with the C1 valve port, the first pump 3321 pumps ultrapure water, and the sample to be measured in the first quantitative ring 3310 is pushed back to the pre-concentration column 3340 to be enriched and concentrated;
s522: after the sample to be tested is enriched and concentrated in the pre-concentration column 3340, the second switching valve 3341 is switched to C2 to be communicated with a C3 valve port, C5 is communicated with a C6 valve port, and the second pump 3331 pumps leacheate to backwash anions on the pre-concentration column 3340 to enter the collection container 335;
s523: the third switching valve 342 is switched to communicate with the port D5 at D6 and with the port D1 at D2. In the conveying unit 350, the third pump 351 extracts the sample to be measured in the collection container 335 and directly enters the second quantitative ring 341 for second quantitative determination;
s524: the third switching valve 342 is switched to communicate with the D5 valve port D4 and communicate with the D1 valve port D2; at the same time, the third pump 351 is activated to send the sample to be measured in the second quantitative ring 341 to the ion chromatograph 400 for analysis.
The ion chromatography system provided by this embodiment separates the sample to be measured containing sulfur ions and not containing sulfur ions in the absorption constant volume module 300, avoids the damage of the hydrogen peroxide remaining in the pipeline to the ion chromatography column, and prolongs the service life of the device.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. An absorption constant volume module is characterized by being used for an ion chromatographic analysis system and comprising a standard sample unit, a collection unit, a primary constant volume unit, a secondary constant volume unit and a conveying unit;
the standard sample unit is used for storing standard samples of ions with different concentrations;
the collecting unit is used for collecting a sample to be detected;
the primary constant volume unit is connected with the collecting unit;
the secondary constant volume unit is respectively connected with the collection unit, the primary constant volume unit and the standard sample unit;
the conveying unit is respectively connected with the standard sample unit, the primary constant volume unit and the secondary constant volume unit;
before the sample to be detected enters an ion chromatograph in the ion chromatographic analysis system for ion chromatographic analysis, the conveying unit is used for pumping the standard sample into the secondary constant volume unit for quantification and conveying the quantified standard sample into the ion chromatograph, and the standard sample is used for calibrating the ion chromatograph and providing reference for the subsequent sample to be detected;
when the collected sample to be detected does not contain sulfur ions, the conveying unit is also used for pumping the sample to be detected into the secondary constant volume unit for quantification and conveying the quantified sample to be detected into the ion chromatograph;
when the collected to-be-detected sample contains sulfur ions, the conveying unit is also used for pumping the to-be-detected sample into the primary constant volume unit for quantification, enrichment and concentration, then the to-be-detected sample enters the secondary constant volume unit for quantification, and then the quantified to-be-detected sample is sent to the ion chromatograph.
2. The absorption constant volume module as claimed in claim 1, wherein the primary constant volume unit comprises a constant quantum unit and a concentration subunit;
the quantitative quantum unit is used for carrying out first quantification on the sample to be detected containing sulfur ions;
the concentration subunit is connected with the quantification subunit, and the concentration subunit is used for enriching and concentrating the sample to be detected after the first quantification.
3. The absorption volumetric module as defined in claim 2, wherein the quantitative sub-unit comprises a first quantitative ring and a multi-channel first switching valve;
two ends of the first quantitative ring are respectively connected with two valve ports of the first switching valve, and the first quantitative ring is used for first quantification of the sample to be detected;
the first switching valve is connected with the collecting unit and the concentrating subunit respectively, and the first switching valve is used for realizing that the first quantitative ring is selectively communicated with the collecting unit or the concentrating subunit.
4. The absorption volumetric module as defined in claim 2, wherein the concentration subunit comprises a pre-concentration column and a multi-channel second switching valve;
two ends of the pre-concentration column are respectively connected with two valve ports of the second switching valve, and the pre-concentration column is used for enriching and concentrating the sample to be tested after first quantification;
the second switching valve is respectively connected with the quantitative subunit and the secondary constant volume unit, and the second switching valve is used for selectively communicating the pre-concentration column with the quantitative subunit or the secondary constant volume unit.
5. The absorption constant volume module according to claim 2, wherein the primary constant volume unit further comprises a collection container, an inlet of the collection container is connected with the concentration subunit, an outlet of the collection container is connected with the secondary constant volume unit, and the collection container is used for collecting the concentrated sample to be tested.
6. The absorption constant volume module as claimed in any one of claims 2 to 5, wherein the primary constant volume unit comprises a first flushing subunit and a second flushing subunit;
the first washing subunit is used for washing the quantitative subunit, the first washing subunit comprises a first cleaning solution container and a first pump, and the first cleaning solution container, the first pump and the quantitative subunit are sequentially connected;
the second washing subunit is used for washing the concentration subunit, the second washing subunit comprises a second cleaning solution container and a second pump, and the second cleaning solution container, the second pump and the concentration subunit are sequentially connected.
7. The absorption constant volume module as claimed in claim 1, wherein the secondary constant volume unit comprises a second constant volume ring and a multi-channel third switching valve;
two ends of the second quantitative ring are respectively connected with two valve ports of the third switching valve;
the third switching valve is respectively connected with the standard sample unit, the collection unit, the primary constant volume unit, the conveying unit and the ion chromatograph, and the third switching valve is used for realizing that the second quantitative ring is selectively communicated with the standard sample unit, the collection unit, the primary constant volume unit, the conveying unit or the ion chromatograph.
8. An ion chromatographic analysis system, which is characterized by comprising an automatic sample feeding module, a high-temperature hydrolysis module, an ion chromatograph and an absorption constant volume module according to any one of claims 1 to 7;
the automatic sample feeding module is used for automatically feeding a sample to the high-temperature hydrolysis module;
the high-temperature hydrolysis module, the absorption constant volume module and the ion chromatograph are sequentially connected.
9. The ion chromatography system of claim 8, wherein the pyrohydrolysis module comprises a combustion furnace, the combustion furnace comprising a housing and a combustion tube, the combustion tube disposed within the housing, the rear cover of the housing being provided with four sets of cooling fans.
10. An ion chromatography method using the ion chromatography system according to any one of claims 8 to 9, the ion chromatography method comprising:
conveying a sample;
carrying out high-temperature hydrolysis on the sample;
condensing and collecting a gaseous sample generated after hydrolysis to obtain a sample to be detected;
calibrating an ion chromatograph through a standard sample;
and quantifying the sample to be detected, and carrying out ion chromatography analysis on the quantified sample to be detected.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110139318.8A CN112505206B (en) | 2021-02-02 | 2021-02-02 | Absorption constant volume module, ion chromatographic analysis system and analysis method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110139318.8A CN112505206B (en) | 2021-02-02 | 2021-02-02 | Absorption constant volume module, ion chromatographic analysis system and analysis method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112505206A CN112505206A (en) | 2021-03-16 |
| CN112505206B true CN112505206B (en) | 2021-04-27 |
Family
ID=74952833
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110139318.8A Active CN112505206B (en) | 2021-02-02 | 2021-02-02 | Absorption constant volume module, ion chromatographic analysis system and analysis method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112505206B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5429946A (en) * | 1991-11-12 | 1995-07-04 | Fisons Instruments S.P.A. | Process and apparatus for elemental analysis of halogens |
| CN101097215A (en) * | 2006-06-29 | 2008-01-02 | 中国石油化工股份有限公司 | Method for measuring SO2 concentration in hydrocarbons gas contained H2S |
| JP2008275327A (en) * | 2007-04-25 | 2008-11-13 | Mitsubishi Chemical Analytech Co Ltd | Analyzer for nitrogen, sulfur and/or halogen in sample |
| CN102778518A (en) * | 2012-07-17 | 2012-11-14 | 东南大学 | Method and device for measuring SOx in fire coal fume |
| CN104931593A (en) * | 2014-03-19 | 2015-09-23 | 内蒙古大唐国际克什克腾煤制天然气有限责任公司 | Method and system for analyzing trace hydrogen sulfide and total chloride in methanation feed gas |
| CN105973666A (en) * | 2016-05-04 | 2016-09-28 | 新奥科技发展有限公司 | Chlorine and sulfur extraction and determination method and apparatus thereof |
| CN106198846A (en) * | 2016-08-31 | 2016-12-07 | 大连博融新材料股份有限公司 | A kind of distillation absorbs chromatography of ions detection electrolyte sulfite radical content method |
| CN106290588A (en) * | 2015-05-12 | 2017-01-04 | 上海宝钢化工有限公司 | NO in a kind of mensuration doctor solution3-the method of content |
| CN110095543A (en) * | 2019-05-17 | 2019-08-06 | 廊坊新奥龙河环保科技有限公司 | The detection method of halogen and sulfur content in a kind of dangerous waste sample |
| CN111337617A (en) * | 2020-03-17 | 2020-06-26 | 安徽国泰众信检测技术有限公司 | Method for detecting sulfite in food |
-
2021
- 2021-02-02 CN CN202110139318.8A patent/CN112505206B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5429946A (en) * | 1991-11-12 | 1995-07-04 | Fisons Instruments S.P.A. | Process and apparatus for elemental analysis of halogens |
| CN101097215A (en) * | 2006-06-29 | 2008-01-02 | 中国石油化工股份有限公司 | Method for measuring SO2 concentration in hydrocarbons gas contained H2S |
| JP2008275327A (en) * | 2007-04-25 | 2008-11-13 | Mitsubishi Chemical Analytech Co Ltd | Analyzer for nitrogen, sulfur and/or halogen in sample |
| CN102778518A (en) * | 2012-07-17 | 2012-11-14 | 东南大学 | Method and device for measuring SOx in fire coal fume |
| CN104931593A (en) * | 2014-03-19 | 2015-09-23 | 内蒙古大唐国际克什克腾煤制天然气有限责任公司 | Method and system for analyzing trace hydrogen sulfide and total chloride in methanation feed gas |
| CN106290588A (en) * | 2015-05-12 | 2017-01-04 | 上海宝钢化工有限公司 | NO in a kind of mensuration doctor solution3-the method of content |
| CN105973666A (en) * | 2016-05-04 | 2016-09-28 | 新奥科技发展有限公司 | Chlorine and sulfur extraction and determination method and apparatus thereof |
| CN106198846A (en) * | 2016-08-31 | 2016-12-07 | 大连博融新材料股份有限公司 | A kind of distillation absorbs chromatography of ions detection electrolyte sulfite radical content method |
| CN110095543A (en) * | 2019-05-17 | 2019-08-06 | 廊坊新奥龙河环保科技有限公司 | The detection method of halogen and sulfur content in a kind of dangerous waste sample |
| CN111337617A (en) * | 2020-03-17 | 2020-06-26 | 安徽国泰众信检测技术有限公司 | Method for detecting sulfite in food |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112505206A (en) | 2021-03-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103048481B (en) | Automatic analyzer for detecting ammonia nitrogen in environmental water and method for detecting ammonia nitrogen in environmental water | |
| CN102253231B (en) | Automatic analyzer of water soluble sulfide and analysis method | |
| US10465853B2 (en) | Ultraclean autosampler with syringe delivery for mass spectrometry | |
| CN112129959B (en) | Full-automatic chemical oxygen demand analyzer based on different liquid transfer flow paths | |
| WO2015139156A1 (en) | Fully automated high-precision capillary electrophoresis instrument | |
| TW201920926A (en) | Automated system for remote inline concentration of ultra-low concentrations in pure chemicals | |
| CN102269732A (en) | High speed electrolyte analysis apparatus | |
| CN104569113A (en) | Hot gas flow dissociation dewatering indirect Karl-Fischer-process analysis device | |
| CN101551323B (en) | Gas phase molecular absorption spectrometer | |
| CN112505206B (en) | Absorption constant volume module, ion chromatographic analysis system and analysis method | |
| CN102253232B (en) | Automatic analyzer and analysis method for water soluble total phosphorus | |
| WO2020087893A1 (en) | Atomic fluorescence spectrometry method and device employing water as carrier fluid | |
| Sabé et al. | Determination of selenium in human blood specimens by electrothermal atomic absorption | |
| CN113270215A (en) | Liquid effluent from nuclear power plants14C automatic pretreatment device and treatment method | |
| US7722822B2 (en) | Sample tube and vial processing system, and method for processing the sample | |
| CN111380942A (en) | Method for determining bromine content in organic photoelectric material based on oxygen bomb combustion method | |
| CN111721609A (en) | Pretreatment device and method for simultaneously treating multiple samples of hydrothermal distillation fluorine | |
| CN103091416B (en) | Gas analyzing system and working method thereof | |
| CN114062522A (en) | Sample pretreatment automation device and method | |
| CN203216909U (en) | Gas analysis system | |
| CN213875430U (en) | Solid organic sample on-line digestion device based on vapor generation-atomic fluorescence spectrometer | |
| CN113711049A (en) | Sample detection device and method for operating sample detection device | |
| CN210953771U (en) | Distilling absorption device for measuring ammonium in sulfuric acid of storage battery | |
| CN220419251U (en) | Anti-adsorption sample injection system for volatile organic compounds | |
| CN217881412U (en) | Analytical equipment of wafer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: Room a708, A701, building 1, 22 Beixing Road (East Section), Daxing District, Beijing 102600 Patentee after: Beikuang Testing Technology Co.,Ltd. Address before: Room a708, A701, building 1, 22 Beixing Road (East Section), Daxing District, Beijing 102600 Patentee before: BGRIMM DETECTION TECHNOLOGY CO.,LTD. |