Interference removal device for measuring anions in high-salt seawater by ion chromatography

Abstract

The invention discloses an interference removal device for measuring high-salt seawater anions through ion chromatography, and relates to the technical field of instrumental analysis, the device comprises at least two working column groups, the working column groups are connected with a chromatograph through conveying pipes, the upper ends of the working column groups are connected with a first pipe body, and electric control valves are arranged at the joints; the working column group comprises a main pretreatment column and an auxiliary pretreatment column which are communicated up and down. The device provided by the invention solves the problems of chromatographic detection signal distortion, short service life of a chromatographic column and difficulty in accurate determination of low-concentration target ions caused by interfering ions in high-salinity seawater in the prior art, and has the advantages of simplicity and convenience in operation, low cost, high automation degree and good compatibility.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of instrumental analysis, in particular to a device for removing interference for ion chromatography determination of anions in high-salt seawater. BACKGROUND

[0002] Ion chromatography, as a kind of high-performance liquid chromatography, is widely used in the field of anion and cation analysis. It realizes ion separation through ion exchange principle, and detects with conductivity, ultraviolet and other detectors, with the advantages of fast analysis speed, good selectivity, and simultaneous determination of multiple components. However, when determining anions in high-salt seawater, many challenges are faced.

[0003] Seawater is called liquid mineral, with an average salinity of 35‰, containing about 35.7 million tons of minerals per cubic kilometer of seawater, and 80% of the known 100 elements can be found in it. The main salts in seawater include a large amount of Cl - and SO4 2⁻ , etc. Based on the existence of high-concentration interfering ions, if direct sampling is performed for ion chromatography analysis, it will cause the conductivity detector to be saturated, the chromatographic column to be unable to work normally due to overload, and the signal of low-concentration target anions (such as nitrate, nitrite, etc.) to be severely masked, making detection difficult to achieve.

[0004] Traditional methods have obvious limitations. Although the dilution method is simple to operate, it will greatly reduce the detection sensitivity, leading to an increase in the detection limit, making it difficult to meet the detection needs of trace anions in seawater; solid-phase extraction requires a large amount of manual operation, the process is complicated, and the resin regeneration is difficult, which is not conducive to large-scale application; online matrix removal technology highly depends on specific instrument equipment, with high cost, and poor compatibility for different types of samples, which is subject to many limitations in actual application. For the existing problems, there are many solutions in the existing technology, such as DE102014226481B3, which realizes multi-way valve unit in gas chromatograph sample metering and separation column switching device, and JP07134120A, which discloses a method and device for ion neutralization. The neutralization treatment device can obtain neutralization treatment according to the treatment of concentrating metal ions in the solution column, and the liquid in the second device discharged from the space in the column to the neutralization treatment, but the above device still has room for improvement in how to more effectively treat Cl - and SO4 2⁻ elements in seawater. SUMMARY

[0005] The application aims to provide an interference removal device for ion chromatography determination of anions in high-salt seawater, solve the problems of distortion of chromatographic detection signal, shortening of service life of a chromatographic column and difficulty in accurate determination of low-concentration target ions caused by interference ions in high-salt seawater in the prior art, and has the advantages of simple operation, low cost, high automation degree and good compatibility.

[0006] To solve the above technical problems, the application specifically provides the following technical scheme: an interference removal device for ion chromatography determination of anions in high-salt seawater, comprising a working column group, the working column group being connected with a chromatograph through a conveying pipe, the working column group being at least two, the upper ends of the working column group being connected with a first pipe body, and an electric control valve being arranged at the connection position, and the working column group comprising a main pretreatment column and a secondary pretreatment column which are in communication.

[0007] The main pretreatment column and the secondary pretreatment column are combined in series, so that the concentration of interference elements in seawater can be reduced to meet the detection requirements of ion chromatography on trace anions, and the problem of covering of a chromatographic signal by a high-salt matrix is solved.

[0008] According to an embodiment of the application, the main pretreatment column and the secondary pretreatment column are both filled with resins, and the loaded cation or anion raw materials in the main pretreatment column and the secondary pretreatment column are different. Different loaded raw materials of different resins can play a role in removing Cl - and SO4 2⁻ elements and cations respectively, and avoid overloading of a single resin column.

[0009] According to an embodiment of the application, the secondary pretreatment column is at least two, and the main pretreatment column is filled with functionalized Ag + loaded sulfonic acid type ion exchange resin, at least one secondary pretreatment column is filled with functionalized Ba 2+ loaded cation resin column, and at least one secondary pretreatment column is filled with functionalized Na + loaded cation resin column. The secondary pretreatment column is at least provided with two, and forms a series process with the main pretreatment column to realize stepwise removal of Cl - and SO4 2⁻ and cations, avoid efficiency reduction of a single resin column caused by overloading of too many types of ions, and support independent replacement of failed resins, reduce maintenance cost, and can flexibly adjust the order of the column group according to fluctuations in salinity of seawater, and adapt to different detection scenes.

[0010] According to an embodiment of the present application, the main pre-treatment column and the auxiliary pre-treatment column are respectively connected with a third pipe body on one side. The third pipe body is in communication with the main pre-treatment column and the auxiliary pre-treatment column on the side, respectively. When the performance of the resin column is monitored to be degraded by the pressure sensor or the conductivity sensor, the high-pressure chromatographic pump can push the backwashing solution to the single column body through the third pipe body, accurately dissolve the AgCl precipitate in the main pre-treatment column or the BaSO4 precipitate in the auxiliary pre-treatment column, and avoid the interference of the regeneration liquid on other column bodies, thereby improving the regeneration efficiency.

[0011] According to an embodiment of the present application, the main pre-treatment column is internally provided with an auxiliary assembly at one end close to the third pipe body. The auxiliary assembly comprises two first filter plates arranged at intervals, the bottom surface of the first filter plate is fixedly connected with a first support rod, and the side of the first support rod is arranged with a second support rod arranged perpendicularly to the axis of the first support rod. The two first filter plates arranged at intervals form a filter sandwich, which can intercept particulate impurities such as silt and biological detritus in seawater, improve the solid particle retention rate of ≥40 μm, and avoid the blockage of resin pores by impurities. At the same time, the porous structure of the filter plate makes the sample flow uniformly dispersed to the resin layer, reduces the local treatment blind area caused by fluid short circuit, and further, the first support rod is vertically fixed to the bottom surface of the filter plate, and the second support rod is radially arranged at intervals and perpendicularly to the first support rod, forming a support frame, which improves the load-bearing capacity of the filter plate and can withstand the fluid impact when pushed by the high-pressure chromatographic pump, thereby avoiding the deformation of the filter plate and the leakage of the resin.

[0012] According to an embodiment of the present application, an annularly arranged first vane plate and an annularly arranged second vane plate are arranged between the two first filter plates. The first vane plate is connected with the surface of one of the first filter plates, the second vane plate is connected with the surface of the other first filter plate, and the first vane plate and the second vane plate are connected through a second ring body. The number of the first vane plates is at least three, which are arranged at intervals around the axis of the first filter plate, and adjacent first vane plates are fixed through a first connecting ring body. The number of the second vane plates is at least three, which are arranged at intervals around the axis of the first filter plate, and adjacent second vane plates are fixed through a third connecting ring body. The first connecting ring body, the second connecting ring body and the third connecting ring body all have through holes in the middle.

[0013] At least 3 first lamella rings are arranged in a ring shape on one side of the first filter plate, and at least 3 second lamella plates are connected through a second ring body to form a multi-layer radial flow channel. When the sample flows, it is cut into multiple streams by the lamella, the contact area between the fluid and the resin is increased, and adjacent first lamella plates are fixed through the first connecting ring body, adjacent second lamella plates are fixed through the third connecting ring body, a stable flow channel frame is formed, the uniformity of the fluid distributed along the column is improved, the state that the flow rate is fast in the center and slow at the edge of the traditional column is avoided, the utilization rate of the resin in the whole column is balanced, further, the through holes in the middle of the first connecting ring body, the second connecting ring body and the third connecting ring body allow the fluid to pass axially, the overall pressure drop increases compared with the structure without lamella, and the flow rate can still be stable when pushed by the high-pressure chromatography pump, thereby avoiding the risk of system overload caused by excessive pressure drop.

[0014] According to an embodiment of the present application, the discharge end of the working column group is provided with a collection container, one end of the collection container is in communication with the auxiliary pretreatment column, and the other end is connected to the sample inlet end of the chromatograph through a conveying pipe. The one end of the collection container is directly communicated with the discharge end of the auxiliary pretreatment column, and the other end is connected to the sample inlet end of the chromatograph through the conveying pipe, which can avoid the pollution risk caused by traditional manual sample transfer, and shorten the time consumption of the detection process.

[0015] According to an embodiment of the present application, the first pipe body is connected with a high-pressure chromatography pump, the high-pressure chromatography pump supplies stable pressure to the working column group to push the high-salt and high-viscosity seawater to quickly pass through the resin column, and the pretreatment time of a single sample is shortened.

[0016] According to an embodiment of the present application, the working column group is installed on the second frame body, the second frame body is provided with a standby column body in communication with the first pipe body, and the first frame body is connected to the bottom of the second frame body, and the chromatograph is installed on the first frame body. The second frame body and the first frame body are connected through the bottom to form a stable base, which avoids loosening of the pipeline or displacement of the resin column caused by vibration, and ensures the stability of fluid transmission.

[0017] According to an embodiment of the present application, the main pretreatment column and the auxiliary pretreatment column are both provided with a pressure sensor and an electric conductivity sensor. When the resin column is used for a long time, the performance of the resin column is judged according to the feedback of the monitoring values of the pressure sensor and the electric conductivity sensor, and the regeneration system is triggered and started, the backwashing solution is pushed by the high-pressure chromatography pump to dissolve the precipitate in the resin column, then pure water is pushed for washing, and then the regeneration liquid is pushed to activate the regenerated resin column.

[0018] Compared with the prior art, the application has the beneficial effects that: the application can reduce the concentration of interfering elements in seawater through the series combination of the main pretreatment column and the auxiliary pretreatment column, meet the detection requirements of ion chromatography on trace anions, and further, the application can dynamically switch according to the use requirements, that is, when one group of working column groups removes ions, the other group of working column groups simultaneously completes backwashing, regeneration and activation, avoiding the need to stop the traditional single column system, the application can solve the problems of signal distortion of chromatographic detection, shortening of the service life of the chromatographic column and difficulty in accurate determination of low-concentration target ions caused by interfering ions in high-salt seawater in the prior art, and has the advantages of simple operation, low cost, high automation and good compatibility. BRIEF DESCRIPTION OF DRAWINGS

[0019] In order to more clearly illustrate the embodiments of the application or the technical solutions in the prior art, the drawings needed to be used in the following embodiment or prior art description will be briefly introduced. Obviously, the drawings in the following description are only exemplary, and other drawings can be obtained according to the provided drawings without creative labor for those skilled in the art.

[0020] Figure 1 A schematic diagram of a device for removing interference of ion chromatography for determining anions in high-salt seawater according to the application; Figure 2 A schematic diagram of a local scheme of a device for removing interference of ion chromatography for determining anions in high-salt seawater according to the application; Figure 3 A schematic diagram of a working column group scheme according to the application; Figure 4 A schematic diagram of the internal structure of a main pretreatment column according to the application; Figure 5 A schematic diagram of an auxiliary assembly scheme according to the application; Figure 6 A schematic diagram of a first support rod and a second support rod scheme according to the application; Figure 7 A schematic diagram of the connection scheme of a first vane, a second vane and a second connecting ring body according to the application; Figure 8 A schematic diagram of the internal structure of a flow control assembly according to the application; Figure 9 A schematic diagram of the working process of a device for removing interference of ion chromatography for determining anions in high-salt seawater; Figure 10 A schematic diagram of the working process of a resin regeneration scheme according to the application.

[0021] Explanation of reference numerals in the attached figures: 10. Chromatograph; 20. First frame; 21. Second frame; 30. Vacuum pump; 40. Controller; 50. First tube; 51. Flow meter; 52. Second tube; 53. Third tube; 60. Working column assembly; 61. Main pretreatment column; 62. Electromagnetic switching valve; 63. Secondary pretreatment column; 64. Collection container; 65. Feed chamber; 70. Spare column; 80. Auxiliary assembly; 81. First filter plate; 82. First support rod; 83. Second support rod; 84. First impeller; 85. First connecting ring; 86. Second connecting ring; 87. Second impeller; 88. Third connecting ring; 90. Flow control assembly; 91. First base; 92. Inlet chamber; 93. Sealing ring; 94. Rubber threaded sleeve; 95. Sliding plug; 96. First spring; 97. Guide plate. Detailed Implementation

[0022] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0023] The concepts involved in this application will first be described with reference to the accompanying drawings. It should be noted that the following descriptions of various concepts are only for the purpose of making the content of this application easier to understand and do not constitute a limitation on the scope of protection of this application; furthermore, the embodiments and features in the embodiments of this application can be combined with each other unless otherwise specified. This application will now be described in detail with reference to the accompanying drawings and embodiments.

[0024] Example 1: As shown in the attached figure Figure 9 Appendix Figure 1 -Appendix Figure 4 As shown, an interference removal device for the determination of anions in high-salt seawater by ion chromatography includes a working column group 60. The working column group 60 is connected to a chromatograph 10 through a delivery pipe. There are at least two working column groups 60. The upper end of each working column group 60 is connected to a first tube body 50, and an electrically controlled valve is provided at the connection. The working column group 60 includes a main pretreatment column 61 and a secondary pretreatment column 63 that are connected vertically.

[0025] This invention reduces the concentration of interfering elements in seawater by combining the main pretreatment column 61 and the secondary pretreatment column 63 in series, thus meeting the requirements for the detection of trace anions in ion chromatography and solving the problem of high-salt matrix masking the chromatographic signal. Furthermore, this invention uses a dual working column group 60 that can be dynamically switched according to usage requirements. That is, when one working column group 60 is performing ion removal, the other working column group 60 simultaneously completes backwashing, regeneration, and activation, avoiding the need to shut down the traditional single-column system.

[0026] Both the main pretreatment column 61 and the auxiliary pretreatment column 63 are filled with resin, but the cationic or anionic raw materials loaded in the main pretreatment column 61 and the auxiliary pretreatment column 63 are different. The different raw materials loaded in different resins enable the separate treatment of Cl... - and SO4 2⁻ Elements and cations work together to prevent overloading of a single resin column.

[0027] As shown in the attached figure Figure 3 As shown, there are at least two secondary pretreatment columns 63, and the main pretreatment column 61 is filled with functionalized Ag with a particle size of 40 μm. + The sulfonic acid-supported ion exchange resin, with at least one secondary pretreatment column 63 containing functionalized Ba with a particle size of 40 μm, is used. 2+ A cation-supported resin column, with at least one secondary pretreatment column 63 containing functionalized Na particles with a particle size of 40 μm. + A cation exchange resin-loaded column is used. At least two secondary pretreatment columns 63 are provided, forming a series flow with the main pretreatment column 61 to achieve Cl... - and SO4 2⁻ It also features stepwise removal of cations, avoiding the efficiency drop caused by loading too many types of ions onto a single resin column; at the same time, the modular resin column design allows for independent replacement of failed resins, reducing maintenance costs, and the column sequence can be flexibly adjusted according to seawater salinity fluctuations to adapt to different detection scenarios.

[0028] As shown in the attached figure Figure 4 As shown, a third tube 53 is connected to one side of both the main pretreatment column 61 and the secondary pretreatment column 63. The third tube 53 is connected to the side of both the main pretreatment column 61 and the secondary pretreatment column 63. When the pressure sensor or conductivity sensor detects a decrease in the performance of the resin column, the high-pressure chromatography pump can push backwash solution directionally to a single column through the third tube 53 to accurately dissolve the AgCl precipitate in the main pretreatment column 61 or the BaSO4 precipitate in the secondary pretreatment column 63, thus avoiding interference of the regeneration solution with other columns and improving regeneration efficiency.

[0029] As shown in the attached figure Figure 4 -Appendix Figure 7As shown, the main pretreatment column 61 is internally provided with an auxiliary assembly 80 near one end of the third tube body 53, and the auxiliary assembly 80 includes two first filter plates 81 arranged at intervals, the bottom surface of the first filter plate 81 is fixedly connected with a first support rod 82, and the side of the first support rod 82 is provided with a second support rod 83 arranged perpendicularly to the axis thereof. The two first filter plates 81 arranged at intervals form a filter sandwich, which can intercept particulate impurities such as silt and biological detritus in seawater, improve the solid particle retention rate of ≥40 μm, and avoid clogging of the resin pores by impurities; at the same time, the porous structure of the filter plate uniformly disperses the sample flow to the resin layer, reduces the local treatment blind area caused by fluid short circuiting, and further, the first support rod 82 is fixed perpendicularly to the bottom surface of the filter plate, and the second support rod 83 is distributed along the radial direction and is perpendicular to the first support rod 82, forming a support frame, which improves the load-bearing capacity of the filter plate and can withstand the fluid impact when the high-pressure chromatography pump is pushed, avoiding deformation of the filter plate caused by resin leakage.

[0030] The first leaf plate 84 and the second leaf plate 87 are arranged in a ring shape and are arranged in a ring shape between the two first filter plates 81, the first leaf plate 84 is connected with the surface of one of the first filter plates 81, the second leaf plate 87 is connected with the surface of the other first filter plate 84, and the first leaf plate 84 and the second leaf plate 87 are connected through the second connecting ring body 86. The number of first leaf plates 84 is at least three, which are arranged around the axis of the first filter plate 81 at intervals, and adjacent first leaf plates 84 are fixed through the first connecting ring body 85. The number of second leaf plates 87 is at least three, which are arranged around the axis of the first filter plate 81 at intervals, and adjacent second leaf plates 87 are fixed through the third connecting ring body 88. The middle part of the first connecting ring body 85, the second connecting ring body 86 and the third connecting ring body 88 has a through hole.

[0031] At least 3 first leaf plates 84 are arranged in a ring shape and arranged on one side of the first filter plate 81, and at least 3 second leaf plates 87 are connected through the second connecting ring body 86, forming a multi-layer radial flow channel. When the sample flow passes through, it is cut into multiple streams by the leaf plate, the contact area between the fluid and the resin is increased, and adjacent first leaf plates 84 are fixed through the first connecting ring body 85, and adjacent second leaf plates 87 are fixed through the third connecting ring body 88, forming a stable flow channel frame, the uniformity of the fluid distributed along the radial direction of the column is improved, avoiding the state that the flow velocity is fast in the center and slow at the edge of the traditional column, ensuring the balanced utilization rate of the resin in the whole column, and further, the through hole in the middle part of the first connecting ring body 85, the second connecting ring body 86 and the third connecting ring body 88 allows the fluid to pass axially, the overall pressure drop increases compared with the structure without the leaf plate, and the flow rate can still be stable when the high-pressure chromatography pump is pushed, avoiding the risk of system overload caused by excessive pressure drop.

[0032] The discharge end of the working column assembly 60 is equipped with a collection container 64. One end of the collection container 64 is connected to the sub-pretreatment column 63, and the other end is connected to the injection end of the chromatograph 10 through a delivery tube. The direct connection between one end of the collection container 64 and the discharge end of the sub-pretreatment column 63, and the connection between the other end and the injection end of the chromatograph 10 through a delivery tube, avoids the risk of contamination caused by traditional manual sample transfer and shortens the detection process time.

[0033] The first tube 50 is connected to a high-pressure chromatography pump, which delivers seawater samples to the working column assembly 60 through the first tube 50. The pump provides stable pressure, which pushes high-salt, high-viscosity seawater through the resin column quickly, thus shortening the pretreatment time for a single sample.

[0034] The working column assembly 60 is mounted on the second frame 21, which has a spare column 70 connected to the first tube 50. The bottom of the second frame 21 is connected to the first frame 20, on which the chromatograph 10 is mounted. The second frame 21 and the first frame 20 form a stable base through the bottom connection, preventing the tubing from loosening or the resin column from shifting due to vibration, and ensuring the stability of fluid transmission.

[0035] Both the main pretreatment column 61 and the auxiliary pretreatment column 63 are equipped with pressure sensors and conductivity sensors. After prolonged use of the resin column, the feedback from the pressure and conductivity sensor readings determines the performance degradation of the resin column, triggering and starting the regeneration system. A high-pressure chromatography pump pushes backwash solution to dissolve the precipitate in the resin column, followed by pure water rinsing, and then regeneration solution to activate and regenerate the resin column.

[0036] Example 2: This embodiment provides an optimized solution based on Embodiment 1. See Appendix. Figure 1 As shown, the second frame 21 is vertically arranged and has two parallel uprights. The two uprights are mounted on the first frame 20 and connected by spaced horizontal bars. This allows for the installation of necessary components on the horizontal bars. The horizontal bars have clamps for assembling the working column assembly 60, fixing the working column assembly 60 to the uprights. In this embodiment, the working column assembly 60 can also be assembled and fixed to the horizontal bars by setting mounting plates or other methods. The two parallel uprights are vertically mounted on the first frame 20 and connected by horizontal bars to form a multi-layered installation plane. The unit floor space is reduced compared to a planar layout, and multiple components such as the working column assembly 60, spare column 70, and high-pressure chromatography pump can be integrated in a limited space. The working column assembly 60 is fixed to the horizontal bars by clamps or mounting plates. The disassembly and assembly time of a single column is shortened to less than 5 minutes, facilitating the rapid replacement of failed resin columns or adjustment of column sequence.

[0037] A controller 40 is fixed on the horizontal rod through an angle plate, the controller 40 is a PLC controller, the controller is connected with the electric control valve, the battery switching valve, the flow meter 51, the vacuum pump 30, the sensor and the chromatograph 10, and is used for realizing accurate control and program optimization. The sensor in the embodiment is a pressure sensor and an electric conductivity sensor, but is not limited to the two sensors, and can also be a temperature sensor, a pH value sensor and the like. The PLC controller 40 is connected with the electric control valve and the electromagnetic switching valve 62, can automatically switch the working column group 60 and the standby column body 70 according to a preset program, the column group switching response time is less than 1 second, the sample processing interruption caused by manual operation delay is avoided, and the high-pressure chromatograph pump is simultaneously linked, and the sample or the regeneration liquid is pushed according to the set flow rate and pressure.

[0038] The device of the application supports multiple preset processing programs, such as high-salt / low-salt seawater mode, and can be switched by one key of the touch screen, the program switching time is less than 5 seconds, and different detection requirements are adapted; and operation data such as pressure, electric conductivity and flow rate are recorded.

[0039] The first frame body 20 has a supporting leg between the bottom and the ground, preferably, a shock pad is arranged on the supporting leg. Specifically, the supporting leg is made of metal and firmly connected with the bottom of the first frame body 20, the single supporting leg has a bearing capacity of greater than or equal to 20 kg, so that the device can remain stationary when the high-pressure chromatograph pump is working, and the loosening of the pipe interface or the deviation of the resin column caused by shaking is avoided.

[0040] The vacuum pump 30 is arranged on the second frame body 21 and connected with the working column group 60 and the standby column body 70 through the second pipe body 52. The vacuum pump 30 generates controllable negative pressure through the second pipe body 52, which can assist the high-pressure chromatograph pump to push the low-viscosity seawater sample to uniformly pass through the resin column, so that the flow rate fluctuation error is reduced, especially for water samples with low salinity or small viscosity, the problem of uneven flow rate in the column caused by self-flow of the fluid is avoided, and the stability of ion removal efficiency is improved.

[0041] Embodiment 3 This embodiment is based on embodiment 1 and further provides an optimization scheme, as shown in FIG. 4, the main pretreatment column 61 and the auxiliary pretreatment column 63 are connected through the electromagnetic switching valve 62, one side of the main pretreatment column 61 and the auxiliary pretreatment column 63 is respectively connected with the third pipe body 53, and the third pipe body 53 is connected with the backwashing pump. Figure 3 The backwashing pump in the embodiment is a high-pressure chromatograph pump, and the main pretreatment column 61 and the auxiliary pretreatment column 63 are connected with the backwashing pump through the third pipe body 53. Figure 9 Figure 10 ​As shown, the pressure sensor and the conductivity sensor in the main pretreatment column 61 and the auxiliary pretreatment column 63 are used for real-time monitoring, and in the case that the pressure or the conductivity is greater than a threshold value, the controller 40 controls the backwashing pump to work and simultaneously cuts off the working column group that is working, specifically through an electrically controlled valve control mode, to switch the working column group 60, so as to keep one group of working column groups 60 in a working state and the other group to be regenerated through backwashing activation, thereby avoiding shutdown.

[0042] Embodiment 4: This embodiment is based on embodiment 1 and further provides an optimization scheme, as shown in the accompanying drawings Figure 4 As shown, the main pretreatment column 61 has a feed chamber 65 separated by a partition plate at the upper portion, and the feed chamber 65 is in communication with the first pipe body 50. The feed chamber 65 is separated from the resin layer of the main pretreatment column 61 by the partition plate, and the sample is uniformly introduced into the resin column by the flow control assembly 90 on the partition plate after entering the chamber through the first pipe body 50, so that the fluid impact velocity is reduced, and the displacement or breakage of resin particles caused by the direct flushing of the resin surface by high-pressure sample flow is avoided.

[0043] A flow control assembly 90 is arranged in the middle of the partition plate, and the flow control assembly 90 comprises a first base body 91, which is a rotary body structure, has a thread on the outer portion, and is provided with a rubber threaded sleeve 94. Threaded holes matched with the rubber threaded sleeve 94 are arranged on the partition plate. An inflow cavity 92 is arranged in the middle of the surface of the first base body 91. A limiting groove is arranged at the bottom of the inflow cavity 92, and a sealing ring 93 is filled in the limiting groove. A pipe through hole penetrating through the bottom of the first base body 91 is arranged below the limiting groove, and a sliding plug 95 is filled in the through hole. An opening allowing the end portion of the sliding plug 95 to pass through is arranged in the middle of the sealing ring 93. The middle of the sliding plug 95 has an outward protruding ring. A guide plate 97 connected with the inner wall of the through hole is fixedly connected in the through hole. The surface of the guide plate 97 is provided with filter holes. A first spring 96 is arranged between the guide plate 97 and the outward protruding ring of the sliding plug 95. Inclined blades are arranged around the inner wall of the through hole.

[0044] The first base body 91 of the present application is installed on the partition plate through the external thread matched with the rubber threaded sleeve 94, so that high-pressure sample leakage can be avoided. The sliding plug 95 in the inflow cavity 92 is subjected to the double actions of the sample pressure and the elastic force of the first spring 96, so that the flow area of the through hole can be automatically adjusted, the flow rate fluctuation can be controlled within ±0.05 mL / min, and the self-adaptive adjustment of the flow rate of 0.1-5 mL / min can be realized when the sample pressure increases or decreases, so that the impact breakage of the resin caused by the sudden change of the flow rate can be avoided.

[0045] Further, the surface filtering holes of the deflector 97 of the present application can trap particle impurities of ≥50 μm in the sample, while the gap between the outer protruding ring of the sliding plug 95 and the deflector 97 forms a turbulent flow area, which, in combination with the cyclone effect generated by the inclined blades on the inner wall of the through hole, improves the uniformity of the flow rate of the sample across the cross section of the resin column, so as to improve the ion exchange efficiency.

[0046] It should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", and the like, indicate an orientation or positional relationship based on the orientation or positional relationship shown in the drawings, and are only used to facilitate the description of the present application and simplify the description, and do not indicate or imply that the device or element referred to must have a particular orientation, be constructed and operated in a particular orientation, and therefore cannot be understood as a limitation on the present application. Unless otherwise expressly defined and limited, the terms "mount", "connect", "connect" and the like should be broadly understood, for example, can be fixedly connected, can be detachably connected, or integrally connected; can be mechanically connected, or electrically connected; can be directly connected, or indirectly connected through an intermediate medium; can be internal communication of two elements. For those skilled in the art, the specific meaning of the above terms in the present application can be understood according to the specific circumstances.

[0047] The above-described embodiments and / or implementations are merely used to illustrate the preferred embodiments and / or implementations of the present application, and do not limit the embodiments of the present application in any form. Any person skilled in the art can make some changes or modifications to other equivalent embodiments without departing from the scope of the technical means disclosed in the present application, but should be considered as substantially the same technology or embodiment as the present application.

[0048] The principles and implementations of the present application are described herein using specific examples. The above example is only used to help understand the method and core idea of the present application. The above description is only the preferred embodiment of the present application. It should be noted that due to the limited nature of the language, there are objectively infinite specific structures. For those skilled in the art, without departing from the principles of the present application, some improvements, refinements or changes can be made, and the above technical features can be combined in an appropriate manner. These improvements, refinements, changes or combinations, or the application of the inventive concept and technical solution to other occasions without improvement, shall be considered as the protection scope of the present application.

Claims

1. A device for removing interference for ion chromatographic determination of anions in high-salt seawater, comprising a working column group (60) connected with a chromatograph (10) through a delivery tube, characterized in that, The working column group (60) is at least two, the upper end of the working column group (60) is connected with the first pipe body (50), and the connection is provided with an electric control valve, the working column group (60) includes the main pretreatment column (61) and the auxiliary pretreatment column (63) which are communicated.

2. The device for removing interference for determination of anions in high-salinity seawater by ion chromatography according to claim 1, characterized in that, The main pretreatment column (61) and the auxiliary pretreatment column (63) are filled with resin, and the main pretreatment column (61) and the auxiliary pretreatment column (63) load different cation or anion raw materials.

3. The device for removing interference of ion chromatography determination of high-salt seawater anions according to claim 1, characterized in that, The said side pre-treatment column (63) is at least two, the main pre-treatment column (61) is filled with functional Ag + The said side pre-treatment column (63) is at least two, the main pre-treatment column (61) is filled with functional Ag 2+ The said side pre-treatment column (63) is at least two, the main pre-treatment column (61) is filled with functional Ag + The said side pre-treatment column (63) is at least two, the main pre-treatment column (61) is filled with functional Ag 4. The device for removing interference of ion chromatography determination of high-salt seawater anions according to claim 1, characterized in that, The main pretreatment column (61) and the auxiliary pretreatment column (63) are connected with the third pipe body (53) on one side.

5. The device for removing interference for ion chromatographic determination of anions in high-salinity seawater according to claim 4, characterized in that, The main pretreatment column (61) is provided with an auxiliary assembly (80) in one end close to the third pipe body (53), the auxiliary assembly (80) includes two first filter plates (81) which are arranged at intervals, the bottom surface of the first filter plate (81) is fixedly connected with a first support rod (82), and the side of the first support rod (82) is provided with a second support rod (83) which is arranged perpendicularly to the axis of the first support rod (82).

6. The device for removing interference of ion chromatography determination of high-salt seawater anions according to claim 5, characterized in that, The first leaf plate (84) and the second leaf plate (87) are arranged in a ring shape between the two first filter plates (81), the first leaf plate (84) is connected with the surface of one of the first filter plates (81), the second leaf plate (87) is connected with the surface of the other first filter plate (84), and the first leaf plate (84) and the second leaf plate (87) are connected through the second connecting ring body (86).

7. The device for removing interference of ion chromatography determination of high-salt seawater anions according to claim 1, characterized in that, The discharge end of the working column group (60) is provided with a collection container (64), one end of the collection container (64) is communicated with the auxiliary pretreatment column (63), and the other end is connected with the sample inlet end of the chromatograph (10) through a conveying pipe.

8. The device for removing interference of ion chromatography determination of high-salt seawater anions according to claim 1, characterized in that, The first pipe body (50) is connected with a high-pressure chromatograph pump.

9. The device for removing interference of ion chromatography determination of high-salt seawater anions according to claim 1, characterized in that, The working column group (60) is installed on the second frame body (21), the second frame body (21) is provided with a standby column body (70) which is communicated with the first pipe body (50), the bottom of the second frame body (21) is connected with the first frame body (20), and the chromatograph (10) is installed on the first frame body (20).

10. The device for removing interference for determination of anions in high-salinity seawater by ion chromatography according to claim 1, characterized in that, The main pretreatment column (61) and the auxiliary pretreatment column (63) are provided with a pressure sensor and an electric conductivity sensor.

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