Miniaturized ion pre-treatment and detection integrated device

Abstract

This invention discloses a miniature integrated ion pretreatment and detection device, including a shell and an external controller. The shell adopts a double-layer composite structure and is made of stainless steel plate. The pretreatment unit and the detection unit are fixedly installed side by side in the upper middle part of the shell, and the temperature control module is fixedly installed in the lower part of the shell by bolts. The external controller is connected to the temperature control module and the detection unit. This device has the characteristics of miniaturization, integration, high sensitivity and low waste liquid discharge.

Description

Technical Field

[0001] This invention belongs to the field of ion separation and detection technology, and relates to a micro ion pretreatment and detection integrated device. Background Technology

[0002] Ion chromatography, as a highly efficient ion separation and detection technique, is widely used in the qualitative and quantitative analysis of inorganic anions and cations. Its core system typically includes a chromatographic column, a pretreatment unit (such as a suppressor), and a detection unit (such as an amperometric detector or a conductivity detector). It also requires auxiliary components such as an eluent tank, a transfer pump, and a waste tank, which are connected sequentially through pipelines to form a complete detection system.

[0003] Publication No. CN106932507B discloses a miniature ion exchange membrane-isolated, high-pressure ion chromatography suppressor, comprising a main regeneration chamber clamp and a secondary regeneration chamber clamp stacked from bottom to top. The electrode surfaces of the main regeneration chamber clamp and the secondary regeneration chamber clamp face each other, and after being pressed together, the multi-layered materials in the middle form a suppressor assembly. The stacked layers between the main regeneration chamber clamp and the secondary regeneration chamber clamp are, from bottom to top, sequentially stacked a main regeneration chamber side sealing sheet with the same shape but different sizes, a main regeneration chamber side ion exchange membrane, an eluent suppression layer, a secondary regeneration chamber side ion exchange membrane, and a secondary regeneration chamber side sealing sheet. The outer dimensions of the ion exchange membrane are generally smaller than the eluent suppression layer, the main regeneration chamber side sealing sheet, and the secondary regeneration chamber side sealing sheet. The ion exchange membrane is isolated and sealed from the outside. The regeneration flow path adopts an internal regeneration liquid channel to connect the main regeneration chamber and the secondary regeneration chamber in series. The main regeneration chamber clamping plate, the main regeneration chamber side sealing plate, and the main regeneration chamber side ion exchange membrane are tightly fitted together to form the main regeneration chamber. The auxiliary regeneration chamber clamping plate, the main regeneration chamber side sealing plate, and the main regeneration chamber side ion exchange membrane are tightly fitted together to form the auxiliary regeneration chamber. The main regeneration chamber clamping plate and the auxiliary regeneration chamber clamping plate are respectively provided with regeneration liquid channel connection ports on their opposite surfaces. The regeneration liquid channel connection pipes are vertically inserted into the main regeneration chamber clamping plate and the auxiliary regeneration chamber clamping plate in sequence. The two ends of the regeneration liquid channel connection pipes are respectively connected to the regeneration liquid channel connection ports. The regeneration liquid channels and the connection pipes are filled with ion exchange resin. The regeneration liquid channel connection pipes are made of PEEK material. The tapered angle of the two ends of the regeneration liquid channel connection pipes is between 45 and 60 degrees. The bottom end of the regeneration liquid channel connection port is a tapered hole with an angle of 50 to 70 degrees. After the suppressor assembly is pressed, the regeneration liquid channels and the two ends of the regeneration liquid channels form a tapered ferrule self-locking structure.

[0004] Publication No. CN209446533U discloses a suppressor for an ion chromatograph, comprising an ion chromatograph housing. The suppressor is located on the right side of the top of the inner cavity of the ion chromatograph housing, and a temperature control warning device is provided on the surface of the suppressor. The temperature control warning device includes a temperature sensor, a controller, a processor, an alarm module, a warning light, and a buzzer. The temperature sensor is fixedly connected to the right side of the center of the front of the suppressor. The controller is fixedly connected to the top right side of the ion chromatograph housing. The processor and the alarm module are fixedly connected sequentially from top to bottom on the front side of the inner cavity of the controller. The warning light is fixedly connected to the right side of the top of the controller. The buzzer is located at the center of the bottom right side of the controller. The output terminal of the temperature sensor is unidirectionally electrically connected to the input terminal of the processor. The output terminal of the processor is unidirectionally electrically connected to the output terminal of the alarm module. The output terminal of the alarm module is unidirectionally electrically connected to the input terminals of the warning light and the buzzer, respectively.

[0005] Existing ion chromatography detection systems suffer from the following technical defects: First, the system structure is fragmented, with the pretreatment unit and detection unit being independent modules. Conventional suppressors are mostly in the 200-400 cm³ range, and conventional detectors are in the 300-500 cm³ range, resulting in a bulky overall size that cannot meet the needs of portability and on-site emergency monitoring. Second, the system equilibration time is long, and the connecting pipelines between the pretreatment and detection modules are long, which not only increases the risk of leakage but also produces extra-column effects, leading to peak broadening and affecting detection accuracy. Third, the eluent consumption is high, generating a large amount of waste liquid, which does not meet the requirements of green and environmentally friendly detection. Fourth, overall temperature control cannot be achieved, and the detection process is significantly affected by ambient temperature, resulting in poor detection stability, especially in trace ion detection scenarios where errors are large. Fifth, the operation process is complex, with the pretreatment and detection modules requiring separate debugging and maintenance, resulting in poor adaptability and difficulty in quickly responding to on-site emergency detection needs.

[0006] Therefore, developing a miniaturized, integrated, highly sensitive, and low-waste-discharge ion pretreatment and detection device to solve the problems of large size, low detection accuracy, and complex operation in existing technologies has become a technical challenge that urgently needs to be addressed by those skilled in the art. Summary of the Invention

[0007] The purpose of this invention is to overcome the shortcomings of the prior art and provide a micro ion pretreatment and detection integrated device, which features miniaturization, integration, high sensitivity and low waste liquid discharge.

[0008] To achieve the above objectives, this invention discloses a micro ion pretreatment and detection integrated device, including a shell and an external controller. The shell adopts a double-layer composite structure and is made of stainless steel plate. The pretreatment unit and the detection unit are fixedly installed side by side in the upper middle part of the shell, and the temperature control module is fixedly installed in the lower part of the shell by bolts. The external controller is connected to the temperature control module and the detection unit.

[0009] Furthermore, the outer shell adopts a double-layer composite structure, with the outer shell made of stainless steel plate and the inner protective layer of the outer shell made of polytetrafluoroethylene material. The temperature control module consists of a miniature heating rod and a PT100 temperature sensor.

[0010] Furthermore, the pretreatment unit includes an ion exchange membrane and two electrodes. The electrodes are deposited on an upper cover plate and a lower cover plate. Both the upper cover plate and the lower cover plate are provided with a regeneration liquid inlet and a regeneration liquid outlet. The two ion exchange membranes are symmetrically distributed between the two electrodes, and a waste liquid channel is formed between the ion exchange membranes and the electrodes. The left side of the sample flow channel formed between the two ion exchange membranes is connected to the outlet of the capillary ion exchange chromatography column through an inlet and a polytetrafluoroethylene pipe. The outlet on the right side of the sample flow channel is connected to the detection unit. The waste liquid channel is connected to an external waste liquid tank through a pipe.

[0011] Furthermore, the electrodes are made of platinum and are deposited on the upper and lower cover plates respectively using sputtering technology.

[0012] Furthermore, both the upper and lower cover plates are made of polyetheretherketone (PEEK).

[0013] Furthermore, the detection unit includes non-contact electrodes, insulating electrodes, and a chip. The chip is fixedly installed inside the housing, and a detection module flow channel is provided inside the chip. Two sets of non-contact electrodes are deposited on the chip using sputtering technology, one near the side of the detection module flow channel, and the insulating electrode is located between the two sets of non-contact electrodes. The liquid outlet of the detection module flow channel is connected to an external waste liquid tank through a pipe, and the outlet on the right side of the sample flow channel is connected to the liquid inlet of the detection module flow channel. The non-contact electrodes are connected to an external controller.

[0014] Furthermore, the chip is a ceramic chip.

[0015] Furthermore, the inlet end of the flow channel of the detection module is provided with a porous ceramic sieve plate, and the outlet on the right side of the sample flow channel is connected to the inlet end of the flow channel of the detection module through the porous ceramic sieve plate.

[0016] Furthermore, the porous ceramic sieve plate has a pore size of 0.3 micrometers.

[0017] Furthermore, the dimensions of the sample flow channel are: 600 micrometers wide, 80 micrometers deep, and 30 millimeters long.

[0018] The present invention has the following beneficial effects: In specific operation, the micro ion pretreatment and detection integrated device of the present invention has a pretreatment unit and a detection unit fixedly installed side by side in the upper middle part of the outer shell, and a temperature control module fixedly installed in the lower part of the outer shell by bolts; the external controller is connected to the temperature control module and the detection unit to realize miniaturized, integrated, highly sensitive and low waste liquid discharge detection, which is extremely practical. Attached Figure Description

[0019] To more clearly illustrate the technical solutions of the embodiments of this application, the drawings used in the description of the embodiments of this application will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0020] Figure 1 This is a structural diagram of the present invention.

[0021] Among them, 1 is the outer shell, 2 is the temperature control module, 3 is the sample flow channel, 4 is the ion exchange membrane, 5 is the electrode, 6 is the non-contact electrode, 7 is the porous ceramic sieve plate, 8 is the insulating electrode, 9 is the chip, 10 is the detection module flow channel, 11 is the liquid inlet, 12 is the waste liquid channel, 51 is the upper cover plate, and 52 is the lower cover 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, not all, of the embodiments of the present invention. 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] In the description of this invention, it should be understood that the terms "comprising" and "including" indicate the presence of the described features, integrals, steps, operations, elements and / or components, but do not exclude the presence or addition of one or more other features, integrals, steps, operations, elements, components and / or collections thereof.

[0024] It should also be understood that the terminology used in this specification is for the purpose of describing particular embodiments only and is not intended to limit the invention. As used in this specification and the appended claims, the singular forms “a,” “an,” and “the” are intended to include the plural forms unless the context clearly indicates otherwise.

[0025] It should also be further understood that the term "and / or" as used in this specification and the appended claims refers to any combination and all possible combinations of one or more of the associated listed items, and includes such combinations. For example, A and / or B can represent three cases: A alone, A and B simultaneously, and B alone. Additionally, the character " / " in this invention generally indicates that the preceding and following objects have an "or" relationship.

[0026] It should be understood that although terms such as first, second, third, etc., may be used in the embodiments of the present invention to describe the preset range, these preset ranges should not be limited to these terms. These terms are only used to distinguish the preset ranges from one another. For example, without departing from the scope of the embodiments of the present invention, the first preset range may also be referred to as the second preset range, and similarly, the second preset range may also be referred to as the first preset range.

[0027] Depending on the context, the word "if" as used here can be interpreted as "when," "when," "in response to determination," or "in response to detection." Similarly, depending on the context, the phrase "if determination" or "if detection (of the stated condition or event)" can be interpreted as "when determination," "in response to determination," "when detection (of the stated condition or event)," or "in response to detection (of the stated condition or event)."

[0028] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, 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, not all, of the embodiments of the present invention. The components of the embodiments of the present invention described and shown in the accompanying drawings can generally be arranged and designed in various different configurations. Therefore, the following detailed description of the embodiments of the present invention provided in the accompanying drawings is not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments of the invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

[0029] The accompanying drawings illustrate various structural schematic diagrams according to embodiments disclosed in this invention. These drawings are not to scale, and some details have been enlarged for clarity, and some details may have been omitted. The shapes of the various regions and layers shown in the drawings, as well as their relative sizes and positional relationships, are merely exemplary and may deviate from reality due to manufacturing tolerances or technical limitations. Furthermore, those skilled in the art can design regions / layers with different shapes, sizes, and relative positions as needed.

[0030] Example 1 refer to Figure 1 The micro ion pretreatment and detection integrated device of the present invention includes a shell 1 and an external controller. The shell 1 adopts a double-layer composite structure. The shell 1 is made of stainless steel plate, and the inner protective layer of the shell 1 is made of polytetrafluoroethylene material, which has signal shielding and heat preservation functions. The pretreatment unit and the detection unit are fixedly installed side by side in the upper middle part of the shell 1. The temperature control module 2 is fixedly installed in the lower part of the shell 1 by bolts. The temperature control module 2 consists of a micro heating rod and a PT100 temperature sensor, with a temperature control range of 25~40℃ and a temperature control accuracy of ±0.5℃. The temperature control module 2, the pretreatment unit and the detection unit are electrically connected to the external controller through wires. The external controller can display temperature, detection signal and other data in real time and supports data storage.

[0031] The pretreatment unit includes an ion exchange membrane 4 and two electrodes 5. The electrodes 5 are made of platinum and are deposited on the upper cover plate 51 and the lower cover plate 52 by sputtering. The upper cover plate 51 and the lower cover plate 52 are both made of polyetheretherketone (PEEK). The surfaces of the upper cover plate 51 and the lower cover plate 52 are provided with regeneration liquid inlet and regeneration liquid outlet, which are obliquely symmetrically distributed and 10 mm away from the edge of the cover plate. The two ion exchange membranes 4 are symmetrically distributed between the two electrodes 5, and a waste liquid channel 12 is formed between the ion exchange membranes 4 and the electrodes 5. A sample flow channel 3 is formed between the two ion exchange membranes 4. The dimensions of the sample flow channel 3 are: width 600 μm, depth 80 μm, and length 30 mm. The left side of the sample flow channel 3 is connected to the outlet of the capillary ion exchange chromatography column through the inlet 11 and the polytetrafluoroethylene pipe. The outlet on the right side of the sample flow channel 3 is connected to the detection unit. The waste liquid channel 12 is connected to an external waste liquid tank through a pipe.

[0032] The detection unit includes a non-contact electrode 6, an insulating electrode 8, and a chip 9. The chip 9 is a ceramic chip, fixedly installed inside the housing 1. A detection module flow channel 10 is provided inside the chip 9. The inlet end of the detection module flow channel 10 is equipped with a porous ceramic sieve plate 7 with a pore size of 0.3 micrometers and an inner diameter of 150 micrometers. Two sets of non-contact electrodes 6 (platinum material) are deposited on the chip 9 using sputtering technology, located near the side of the detection module flow channel 10. The insulating electrode 8 (alumina material) is located between the two sets of non-contact electrodes 6. The outlet end of the detection module flow channel 10 is connected to an external waste liquid tank via a pipe. The outlet on the right side of the sample flow channel 3 is connected to the inlet end of the detection module flow channel 10 via the porous ceramic sieve plate 7. The non-contact electrode 6 and the temperature control module 2 are connected to an external controller.

[0033] The working process of this embodiment is as follows: The external controller presets the temperature of the temperature control module 22 to 30℃. The temperature control module 2 is activated, stabilizing the temperature of the pretreatment unit and the detection unit at 30℃±0.5℃. The anionic mixed sample containing chloride ions and fluoride ions is separated by the eluent through the capillary ion exchange chromatography column and enters the sample flow channel 3 through the pipeline. In the pretreatment unit, the ion exchange membrane 4 and the electrode 5 work together to separate the impurity ions in the eluent to the waste liquid channel 12 and discharge it to the waste liquid tank. The target ions (chloride ions and fluoride ions) enter the detection module flow channel 10 with the liquid. The non-contact electrode 6 detects the electrical signal corresponding to the ion concentration. After passing through the insulating electrode 8 to avoid interference, the signal is transmitted to the external controller. The external controller processes the signal to obtain the concentration data of chloride ions and fluoride ions, thus completing the detection.

[0034] Tests showed that the device in this embodiment has a volume of 80 cm³, a system equilibration time of 8 minutes, a 60% reduction in rinsing fluid consumption compared to existing technologies, a 35% increase in detection sensitivity, and a detection error of ±1.5%, effectively enabling rapid and accurate detection of trace anions.

[0035] Example 2 The difference between this embodiment and Embodiment 1 is that: the electrode 5 is made of titanium; the sample flow channel 3 has a width of 400 micrometers, a depth of 50 micrometers, and a length of 20 millimeters; the inner diameter of the flow channel 10 of the detection module is 50 micrometers; the aperture of the sieve plate 7 is 0.2 micrometers; the preset temperature of the temperature control module 2 is 25°C; and the distance between the regenerated liquid inlet and the regenerated liquid outlet and the edge of the cover plate is 5 millimeters.

[0036] Tests showed that the device in this embodiment has a volume of 50 cm³, a system equilibration time of 6 minutes, a 55% reduction in rinsing fluid consumption, a 30% increase in detection sensitivity, and a detection error of ±1.8%, making it suitable for portable trace ion detection equipment.

[0037] Example 3 The difference between this embodiment and Embodiment 1 is that: the electrode 5 is made of platinum-titanium alloy, the sample flow channel 33 has a width of 800 micrometers, a depth of 100 micrometers, and a length of 50 millimeters; the inner diameter of the flow channel 10 of the detection module is 300 micrometers, and the aperture of the sieve plate 7 is 0.5 micrometers; the preset temperature of the temperature control module 2 is 40°C, and the distance between the regeneration liquid inlet and the regeneration liquid outlet and the edge of the cover plate is 20 millimeters.

[0038] Tests showed that the device in this embodiment has a volume of 100 cm³, a system equilibration time of 10 minutes, a 50% reduction in rinsing fluid consumption, a 40% increase in detection sensitivity, and a detection error of ±1.2%, making it suitable for high-sensitivity trace ion detection scenarios.

[0039] This invention has the following characteristics: 1) Integrated design and miniaturized size: The present invention integrates the pretreatment unit and the detection unit in the same shell 1, abandoning the traditional distributed module design. The overall volume is reduced to 50~100cm³, which is much smaller than the volume of existing independent modules. It can be adapted to portable detection equipment and meet the needs of on-site emergency monitoring.

[0040] 2) High detection accuracy and good stability: This invention effectively reduces extra-column effects and avoids chromatographic peak broadening by shortening the connecting pipeline between the pretreatment and detection modules; at the same time, the temperature control module 2 is set up to achieve precise temperature control, reduce the influence of ambient temperature on the detection results, improve the detection sensitivity by more than 30% compared with the existing technology, and control the detection error within ±2%.

[0041] 3) Green and environmentally friendly with less waste discharge: The sample flow channel 3 and the detection module flow channel 10 adopt a miniaturized design, which reduces the sample volume and rinsing solution consumption by more than 50% and significantly reduces the amount of waste liquid generated, which is in line with the green and environmentally friendly detection concept; at the same time, the electrodes can be regenerated online through regeneration solution, extending their service life and reducing the cost of use.

[0042] 4) Short system balancing time and convenient operation: The integrated structure reduces the number of connecting pipes and debugging steps, shortening the system balancing time to less than 10 minutes, which greatly improves the detection efficiency compared with the existing technology (balancing time of more than 30 minutes); the device is easy to disassemble and clean, and the maintenance cost is low.

[0043] 5) High adaptability and wide range of applications: This invention can be used with capillary ion exchange chromatography columns of different specifications, and is suitable for the detection of trace inorganic anions and cations in environmental water samples, biopharmaceutical samples and food samples, and is suitable for a variety of detection scenarios.

[0044] Other embodiments of the invention will readily occur to those skilled in the art upon consideration of the specification and disclosure of the invention. This application is intended to cover any variations, uses, or adaptations of the invention that follow the general principles of the invention and include common knowledge or customary techniques in the art not disclosed herein. The specification and examples are to be considered exemplary only, and the true scope and spirit of the invention are indicated by the following claims.

[0045] It should be understood that the present invention is not limited to the precise structure described above and shown in the accompanying drawings, and various modifications and changes can be made without departing from its scope. The scope of the invention is limited only by the appended claims.

[0046] The above description is merely a preferred embodiment of the present invention and does not constitute any limitation on the present invention. Any simple modifications, alterations, or equivalent structural changes made to the above embodiments based on the technical essence of the present invention shall still fall within the protection scope of the present invention.

Claims

1. A micro-ion pretreatment and detection integrated device, characterized in that, Includes a housing (1) and an external controller. The housing (1) adopts a double-layer composite structure. The housing (1) is made of stainless steel plate. The pretreatment unit and the detection unit are fixedly installed side by side in the upper middle part of the housing (1). The temperature control module (2) is fixedly installed in the lower part of the housing (1). The external controller is connected to the temperature control module (2) and the detection unit.

2. The integrated micro ion pretreatment and detection device according to claim 1, characterized in that, The outer shell (1) adopts a double-layer composite structure. The outer shell (1) is made of stainless steel plate. The inner protective layer of the outer shell (1) is made of polytetrafluoroethylene material. The temperature control module (2) consists of a miniature heating rod and a PT100 temperature sensor.

3. The integrated micro ion pretreatment and detection device according to claim 1, characterized in that, The pretreatment unit includes an ion exchange membrane (4) and two electrodes (5). The electrodes (5) are deposited on the upper cover plate (51) and the lower cover plate (52). The surfaces of the upper cover plate (51) and the lower cover plate (52) are provided with a regeneration liquid inlet and a regeneration liquid outlet. The two ion exchange membranes (4) are symmetrically distributed between the two electrodes (5). A waste liquid channel (12) is formed between the ion exchange membranes (4) and the electrodes (5). The left side of the sample flow channel (3) formed between the two ion exchange membranes (4) is connected to the outlet of the capillary ion exchange chromatography column through the inlet (11) and the polytetrafluoroethylene pipe. The outlet on the right side of the sample flow channel (3) is connected to the detection unit. The waste liquid channel (12) is connected to the external waste liquid tank through the pipe.

4. The integrated micro ion pretreatment and detection device according to claim 3, characterized in that, The electrode (5) is made of platinum material and is deposited on the upper cover plate (51) and the lower cover plate (52) by sputtering technology.

5. The integrated micro ion pretreatment and detection device according to claim 3, characterized in that, Both the upper cover plate (51) and the lower cover plate (52) are made of polyetheretherketone (PEEK).

6. The integrated micro ion pretreatment and detection device according to claim 3, characterized in that, The detection unit includes a non-contact electrode (6), an insulating electrode (8), and a chip (9). The chip (9) is fixedly installed inside the housing (1). The chip (9) has a detection module flow channel (10). Two sets of non-contact electrodes (6) are deposited on the chip (9) by sputtering technology, close to the side of the detection module flow channel (10). The insulating electrode (8) is located in the middle of the two sets of non-contact electrodes (6). The liquid outlet of the detection module flow channel (10) is connected to an external waste liquid tank through a pipe. The outlet on the right side of the sample flow channel (3) is connected to the liquid inlet of the detection module flow channel (10). The non-contact electrode (6) is connected to an external controller.

7. The integrated micro ion pretreatment and detection device according to claim 6, characterized in that, Chip (9) is a ceramic chip.

8. The integrated micro ion pretreatment and detection device according to claim 6, characterized in that, The inlet end of the flow channel (10) of the detection module is provided with a porous ceramic sieve plate (7), and the outlet on the right side of the sample flow channel (3) is connected to the inlet end of the flow channel (10) of the detection module via the porous ceramic sieve plate (7).

9. The integrated micro ion pretreatment and detection device according to claim 8, characterized in that, The porous ceramic sieve plate (7) has a pore size of 0.3 micrometers.

10. The integrated micro ion pretreatment and detection device according to claim 3, characterized in that, The dimensions of the sample flow channel (3) are: 600 micrometers wide, 80 micrometers deep, and 30 millimeters long.

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