Double-membrane leacheate generator and chromatographic detection equipment

Abstract

The invention provides a double-membrane type leacheate generator and chromatographic detection equipment. The double-membrane leacheate generator comprises a stock solution channel, a first ion exchange membrane group is arranged between the leacheate channel and the stock solution channel, and the first ion exchange membrane group comprises at least one ion exchange membrane; a second ion exchange membrane group is arranged among the regeneration liquid channel, the leacheate channel and the regeneration liquid channel, the second ion exchange membrane group comprises a bipolar membrane, hydrogen ions or hydroxyl ions generated after the regeneration liquid at the bipolar membrane is electrolyzed correspondingly enter different sides of the bipolar membrane, and impurity ions are prevented from entering the leacheate channel through the bipolar membrane. The chromatographic detection equipment provided by the invention comprises the double-membrane type leacheate generator. The bipolar membrane is applied between the regeneration channel and the leacheate channel, corresponding hydrogen ions or hydroxyl ions can be provided for the leacheate channel, impurity ions in regeneration liquid can be prevented from entering the leacheate channel, and the purity of the leacheate is improved.

Description

Technical Field

[0001] The present application relates to the technical field of analytical instruments and equipment, and in particular to a double-membrane eluent generator and a chromatographic detection device. Background Art

[0002] See also Figure 1 , Figure 2 In a double-membrane eluent generator known to the inventor of the present application, taking KOH type eluent as an example, the eluent generator 5 is divided by a cation exchange membrane 61 and an anion exchange membrane 62 into an eluent channel 63 and a raw liquid channel 64 and a regeneration liquid channel 65 on both sides thereof.

[0003] KOH as the stock solution is directly connected to the stock solution channel 64. The eluent in the eluent channel 63 is connected to the regeneration solution channel 65 as the regeneration solution after subsequent use. The K+ in the stock solution channel 64 enters the eluent channel 63 through the cation exchange membrane 61, and the OH- generated by the electrolysis of water in the regeneration solution channel 65 enters the eluent channel 63 through the anion exchange membrane 62.

[0004] The double membrane eluent generator uses the used eluent. However, the used eluent may contain impurity ions in the test sample. Such impurity ions will re-enter the eluent through the ion exchange membrane, resulting in low eluent purity and interference with subsequent analytical experiments. Summary of the invention

[0005] In order to improve or solve at least one technical problem mentioned in the background technology, the present application provides a double-membrane eluent generator and a chromatographic detection device.

[0006] The double-membrane eluent generator provided in the embodiment of the present application includes a first eluent generator, and the first eluent generator includes:

[0007] A stock solution channel, wherein the stock solution provides anions or cations for the eluent;

[0008] An eluent channel, wherein water passes through the eluent channel to form the eluent, a first ion exchange membrane group is disposed between the eluent channel and the stock solution channel, the first ion exchange membrane group includes at least one ion exchange membrane, the ion exchange membrane is a cation exchange membrane or an anion exchange membrane, and the cations or anions in the stock solution pass through the first ion exchange membrane group into the eluent channel;

[0009] A regeneration liquid channel, wherein the eluent enters the regeneration liquid channel after use and becomes the regeneration liquid, a second ion exchange membrane group is arranged between the eluent channel and the regeneration liquid channel, the second ion exchange membrane group includes a bipolar membrane, hydrogen ions or hydroxide ions generated after electrolysis of the regeneration liquid at the bipolar membrane can enter different sides of the bipolar membrane accordingly, and the bipolar membrane can prevent impurity ions other than the hydrogen ions or the hydroxide ions from passing through the bipolar membrane into the eluent channel.

[0010] In at least one embodiment, the second ion exchange membrane group further includes at least one cation exchange membrane or anion exchange membrane stacked together with the bipolar membrane.

[0011] In at least one embodiment, one of the positive electrode and the negative electrode is placed in the raw solution channel, and the other of the positive electrode or the negative electrode is placed in the regeneration solution channel.

[0012] In at least one embodiment, the double-membrane eluent generator further comprises a second eluent generator, wherein the second eluent generator comprises an eluent channel.

[0013] The eluent channel of the first eluent generator is connected to the eluent channel of the second eluent generator, so that the eluent generated by the first eluent generator can be further adjusted.

[0014] In at least one embodiment, the second eluent generator has the same structure as the first eluent generator.

[0015] The stock solution channel of the first eluent generator and the stock solution channel of the second eluent generator are not connected and are respectively supplied with corresponding stock solutions.

[0016] The regeneration liquid channel of the first eluent generator is connected to the regeneration liquid channel of the second eluent generator,

[0017] The eluent passes through the eluent channel of the first eluent generator and the eluent channel of the second eluent generator in sequence, and then is used to form the regeneration liquid. The regeneration liquid then passes through the regeneration liquid channel of the second eluent generator and the regeneration liquid channel of the first eluent generator in sequence to form waste liquid for discharge.

[0018] In at least one embodiment, both sides of the eluent channel of the second eluent generator are regeneration liquid channels, and the used eluent is formed into the regeneration liquid and passes through the regeneration liquid channels on both sides of the eluent channel of the second eluent generator and the regeneration liquid channel of the first eluent generator to form waste liquid for discharge.

[0019] In at least one embodiment, the second eluent generator is divided into the eluent channel and the regeneration liquid channels on both sides thereof by two groups of the second ion exchange membrane groups.

[0020] The chromatographic detection device provided in the embodiment of the present application includes the double-membrane eluent generator as described above.

[0021] In at least one embodiment, the chromatographic detection device further comprises a water source, a pump, an injector, a chromatographic column, a suppressor, and a detector.

[0022] Under the action of the pump, the water provided by the water source enters the eluent channel to form the eluent, and the eluent passes through the injector, the chromatographic column, the suppressor, and the detector to enter the regeneration liquid channel to form the regeneration liquid, and then becomes waste liquid after electrolysis and is discharged from the regeneration liquid channel.

[0023] In at least one embodiment, the chromatographic detection device further comprises a stock solution bottle and a stock solution pump, and under the action of the stock solution pump, the stock solution circulates between the stock solution bottle and the stock solution channel, or

[0024] The raw liquid bottle is directly connected to the raw liquid channel.

[0025] The double-membrane eluent generator provided in the present application applies a bipolar membrane between the regeneration channel and the eluent channel of the double-membrane eluent generator, which can not only provide the corresponding H+ or OH- to the eluent channel through the electrolytic regeneration liquid, but also block the impurity ions in the regeneration liquid from entering the eluent channel, thereby improving the purity of the eluent.

[0026] The chromatographic detection equipment provided in the present application includes the above-mentioned double-membrane eluent generator and also has the above-mentioned advantages. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 A schematic structural diagram of a chromatographic detection device including a double-membrane eluent generator is shown.

[0028] Figure 2 Shows Figure 1 Schematic diagram of the double membrane eluent generator in .

[0029] Figure 3 , Figure 4 , Figure 5 , Figure 6 The schematic diagrams of the structures of four embodiments of the chromatographic detection device including a double-membrane eluent generator according to the embodiment of the present application are shown.

[0030] Figure 7 , Figure 8 A schematic diagram of a double-membrane eluent generator according to an embodiment of the present application is shown.

[0031] Description of Reference Numerals

[0032] 1 first eluent generator; 11 raw liquid channel; 12 eluent channel; 13 regeneration liquid channel;

[0033] 2 second eluent generator; 21 raw liquid channel; 22 eluent channel; 23 regeneration liquid channel; 24 regeneration liquid channel;

[0034] 3 first ion exchange membrane group; 31 ion exchange membrane;

[0035] 4 a second ion exchange membrane group; 41 a bipolar membrane;

[0036] 5. Eluent generator;

[0037] 61 cation exchange membrane; 62 anion exchange membrane; 63 eluent channel; 64 raw liquid channel; 65 regeneration liquid channel;

[0038] 71 water source unit; 72 pump; 73 injector; 74 chromatographic column; 75 suppressor; 76 detector; 77 stock solution bottle; 78 stock solution pump. DETAILED DESCRIPTION

[0039] The exemplary embodiments of the present application are described below with reference to the accompanying drawings. It should be understood that these specific descriptions are only used to teach those skilled in the art how to implement the present application, and are not intended to exhaust all possible methods of the present application, nor to limit the scope of the present application.

[0040] The bipolar membrane is an ion exchange membrane with a special ion structure made of a composite of a cation membrane and an anion membrane, which is impermeable to both anions and cations. However, under the action of a DC electric field, the H2O between the composite layer of the anion membrane and the cation membrane in the bipolar membrane dissociates into H+ and OH- and can enter the corresponding side of the bipolar membrane through the cation membrane and the anion membrane respectively. Therefore, the bipolar membrane is applied between the regeneration channel and the eluent channel of the bipolar membrane eluent generator, which can not only provide the eluent channel with the corresponding H+ or OH- through the electrolytic regeneration liquid, but also prevent the impurity ions in the regeneration liquid from entering the eluent channel.

[0041] The present application provides a double-membrane eluent generator and a chromatographic detection device, which embody the above-mentioned ideas.

[0042] Below, this application provides several embodiments.

[0043] Example 1

[0044] See also Figure 3Embodiment 1 provides a double membrane type eluent generator, which includes a first eluent generator 1. The first eluent generator 1 includes a raw liquid channel 11, an eluent channel 12 and a regeneration liquid channel 13.

[0045] The stock solution in the stock solution channel 11 provides the eluent with the required high-concentration anions or cations, such as potassium ions.

[0046] The water (e.g., pure water) in the eluent channel 12 forms an eluent after passing through the eluent channel 12. A first ion exchange membrane group 3 is disposed between the eluent channel 12 and the stock solution channel 11, and the first ion exchange membrane group 3 includes at least one ion exchange membrane 31. The ion exchange membrane 31 is a cation exchange membrane or anion exchange membrane, and the cations or anions in the stock solution enter the eluent channel 12 through the first ion exchange membrane group 3.

[0047] After being used, the eluent enters the regeneration liquid channel 13 to become the regeneration liquid, and a second ion exchange membrane group 4 is arranged between the eluent channel 12 and the regeneration liquid channel 13. The second ion exchange membrane group 4 includes a bipolar membrane 41, and the hydrogen ions or hydroxide ions generated after the electrolysis of the regeneration liquid at the bipolar membrane 41 can enter the different sides of the bipolar membrane 41 accordingly, and the bipolar membrane 41 can prevent the impurity ions other than hydrogen ions or hydroxide ions from passing through the bipolar membrane 41 to enter the eluent channel 12. It can be understood that the eluent being used can refer to the eluent being tested by subsequent equipment such as an injector, a chromatographic column, and a detector.

[0048] For example, see Figure 7 When the eluent is required to be KOH, for example, the ion exchange membrane 31 may be a cation exchange membrane, through which K+ in the stock solution channel 11 can enter the eluent channel 12. The membrane of the bipolar membrane 41 facing the eluent channel 12 is a cationic membrane, and the OH- generated by the electrolysis of water in the bipolar membrane 41 can enter the eluent channel 12 through its cationic membrane, and blocks other impurity ions from entering the eluent channel 12, so that the eluent has a higher purity and fewer impurities.

[0049] For example, see Figure 8 When the eluent is required to be, for example, MSA (methanesulfonic acid, chemical formula CH4O3S), the ion exchange membrane 31 may be an anion exchange membrane, and the anions of the MSA in the raw liquid channel 11 ( Figure 8 MSA- in the figure represents the anion of MSA) can enter the eluent channel 12 through the anion exchange membrane. The membrane of the bipolar membrane 41 facing the eluent channel 12 is a cationic membrane. The H+ generated after the electrolysis of water in the bipolar membrane 41 can enter the eluent channel 12 through its cationic membrane, and blocks other impurity ions from entering the eluent channel 12, so that the eluent has a higher purity.

[0050] It can be understood that the application of the above-mentioned ion exchange membrane and eluent is only an example, and the present application does not limit the specific types of eluent and ion exchange membrane.

[0051] Further, see Figure 7 , Figure 8 The second ion exchange membrane group 4 may include at least one cation exchange membrane or anion exchange membrane stacked with the bipolar membrane 41. The first ion exchange membrane group 3 may also be composed of a plurality of stacked ion exchange membranes 31. It can be understood that the structure of stacking multiple membranes is conducive to increasing the mechanical strength and durability of the membrane.

[0052] Further, see Figure 3 , one of the positive electrode and the negative electrode is placed in the stock solution channel 11, and the other of the positive electrode or the negative electrode is placed in the regeneration solution channel 13. The positive electrode and the negative electrode can be connected to a constant current power supply, respectively. It can be understood that the present application does not limit the specific positions of the positive electrode and the negative electrode, and the electrode positions can be reasonably set according to the stock solution type and the position of each channel. By controlling the current value set by the constant current power supply, the amount of water electrolysis and ion migration can be controlled, thereby controlling the concentration of the eluent.

[0053] See also Figure 3 The chromatographic detection equipment provided in the present application may include the above-mentioned double-membrane eluent generator, a water source part 71, a pump 72, an injector 73, a chromatographic column 74, a suppressor 75, a detector 76, a stock solution bottle 77, and a stock solution pump 78.

[0054] Driven by the pump 72, water (such as pure water) provided by the water source 71 enters the eluent channel 12 to form an eluent, and the eluent passes through the injector 73, the chromatographic column 74, the suppressor 75, and the detector 76 into the regeneration liquid channel 13 to form a regeneration liquid. The regeneration liquid is discharged after being electrolyzed.

[0055] Driven by the stock liquid pump 78, the stock liquid can circulate in the stock liquid bottle 77 and the stock liquid channel 11, and the circulation process can drive the flow of bubbles to avoid bubble aggregation and affect the electrolysis process. In addition, compared with the solution in which both sides of the eluent channel are set as stock liquid channels, the stock liquid channel in the present application is relatively short, and the stock liquid pump 78 only needs to remove the bubbles in one side of the channel, the rotation speed of the stock liquid pump 78 can be reduced, and the noise can be reduced. Exemplarily, the stock liquid pump 78 can be a peristaltic pump.

[0056] Example 2

[0057] Compared to Figure 3 Example 1 shown, Figure 4The double membrane eluent generator of Example 2 itself is shown to be unchanged. The improvement of Example 2 lies in the connection mode between the stock liquid bottle and the stock liquid channel. Specifically, the stock liquid bottle 77 can be directly connected to the stock liquid channel 11, and no circulation occurs in the channel. The bubbles in the stock liquid channel 11 can directly enter the stock liquid bottle 77 or be discharged through the stock liquid bottle 77, thereby reducing the number of pumps.

[0058] Embodiment 3, 4

[0059] See also Figure 5 , Figure 6 The double membrane type eluent generator may further include a second eluent generator 2, and the second eluent generator 2 includes an eluent channel 22. The eluent channel 12 of the first eluent generator 1 is connected to the eluent channel 22 of the second eluent generator 2, so that the eluent generated by the first eluent generator 1 can be further adjusted.

[0060] In Example 3, see Figure 5 The second eluent generator 2 has the same structure as the first eluent generator 1 .

[0061] The stock solution channel 11 of the first eluent generator 1 and the stock solution channel 21 of the second eluent generator 2 are not connected and are respectively supplied with corresponding stock solutions. The types of the stock solutions can be the same.

[0062] The regeneration liquid channel 13 of the first eluent generator 1 is connected to the regeneration liquid channel 23 of the second eluent generator 2. The eluent passes through the eluent channel 12 of the first eluent generator 1 and the eluent channel 22 of the second eluent generator 2 in sequence, and then is used to form a regeneration liquid. The regeneration liquid then passes through the regeneration liquid channel 23 of the second eluent generator 2 and the regeneration liquid channel 13 of the first eluent generator 1 in sequence to form a waste liquid for discharge.

[0063] In Example 4, see Figure 6 There are regeneration liquid channels 24 on both sides of the eluent channel 22 of the second eluent generator 2. The used eluent is formed into regeneration liquid and passes through the regeneration liquid channels 24 on both sides of the eluent channel 22 of the second eluent generator 2 and the regeneration liquid channel 13 of the first eluent generator 1 to form waste liquid for discharge.

[0064] The second eluent generator 2 can be divided into an eluent channel 22 and two regeneration liquid channels 24 on both sides thereof by two groups of second ion exchange membrane groups 4 .

[0065] In Examples 3 and 4, the second eluent generator 2 is equivalent to being able to make secondary adjustments to the eluent, and can control the type and concentration of its stock solution (Example 3) to control the degree of electrode electrolysis of water, thereby adjusting the pH, concentration and other parameters of the eluent.

[0066] Of course, more usage modes can be expanded by connecting more eluent generators and changing the connection mode of the eluent channels and the regeneration liquid channels between the eluent generators.

[0067] The chromatographic detection equipment provided in the present application may be a liquid chromatography detection equipment, an ion chromatography detection equipment, etc.

[0068] The above is a preferred embodiment of the present application. It should be pointed out that for those skilled in the art, several improvements and modifications can be made without departing from the principles of the present application. These improvements and modifications should also be regarded as the scope of protection of the present application.

Claims

1. A double membrane eluent generator, characterized in that: The invention comprises a first eluent generator (1), wherein the first eluent generator (1) comprises: A stock solution channel (11), wherein the stock solution provides anions or cations for the eluent; An eluent channel (12), wherein water passes through the eluent channel (12) to form the eluent, a first ion exchange membrane group (3) is arranged between the eluent channel (12) and the stock solution channel (11), the first ion exchange membrane group (3) comprising at least one ion exchange membrane (31), the ion exchange membrane (31) being a cation exchange membrane or an anion exchange membrane, and the cations or anions in the stock solution pass through the first ion exchange membrane group (3) into the eluent channel (12); A regeneration liquid channel (13), wherein the eluent enters the regeneration liquid channel (13) after use to become the regeneration liquid, a second ion exchange membrane group (4) is arranged between the eluent channel (12) and the regeneration liquid channel (13), the second ion exchange membrane group (4) includes a bipolar membrane (41), hydrogen ions or hydroxide ions generated after electrolysis of the regeneration liquid at the bipolar membrane (41) can enter different sides of the bipolar membrane (41) respectively, and the bipolar membrane (41) can prevent impurity ions other than the hydrogen ions or the hydroxide ions from passing through the bipolar membrane (41) into the eluent channel (12).

2. The double membrane eluent generator according to claim 1, characterized in that: The second ion exchange membrane group (4) further comprises at least one cation exchange membrane or anion exchange membrane stacked together with the bipolar membrane (41).

3. The double membrane eluent generator according to claim 1, characterized in that: One of the positive electrode and the negative electrode is placed in the raw liquid channel (11), and the other of the positive electrode or the negative electrode is placed in the regeneration liquid channel (13).

4. The double membrane eluent generator according to claim 1, characterized in that: The double-membrane eluent generator further comprises a second eluent generator (2), wherein the second eluent generator (2) comprises an eluent channel (22). The eluent channel (12) of the first eluent generator (1) and the eluent channel (22) of the second eluent generator (2) are connected, so that the eluent generated by the first eluent generator (1) can be further adjusted.

5. The double membrane eluent generator according to claim 4, characterized in that: The second eluent generator (2) has the same structure as the first eluent generator (1). The stock solution channel (11) of the first eluent generator (1) and the stock solution channel (21) of the second eluent generator (2) are not connected and are respectively supplied with corresponding stock solutions. The regeneration liquid channel (13) of the first eluent generator (1) is connected to the regeneration liquid channel (23) of the second eluent generator (2), The eluent passes through the eluent channel (12) of the first eluent generator (1) and the eluent channel (22) of the second eluent generator (2) in sequence, and is then used to form the regeneration liquid. The regeneration liquid then passes through the regeneration liquid channel (23) of the second eluent generator (2) and the regeneration liquid channel (13) of the first eluent generator (1) in sequence, and is then discharged as waste liquid.

6. The double membrane eluent generator according to claim 4, characterized in that: Both sides of the eluent channel (22) of the second eluent generator (2) are regeneration liquid channels (24). The used eluent is converted into the regeneration liquid and passes through the regeneration liquid channels (24) on both sides of the eluent channel (22) of the second eluent generator (2) and the regeneration liquid channel (13) of the first eluent generator (1) to form waste liquid for discharge.

7. The double membrane eluent generator according to claim 6, characterized in that: The second eluent generator (2) is divided into the eluent channel (22) and the regeneration liquid channels (24) on both sides thereof by two groups of the second ion exchange membrane groups (4).

8. A chromatographic detection device, characterized in that: The invention comprises the double membrane eluent generator according to any one of claims 1 to 7.

9. The chromatographic detection device according to claim 8, characterized in that: The chromatographic detection device further comprises a water source (71), a pump (72), an injector (73), a chromatographic column (74), a suppressor (75), and a detector (76). Under the action of the pump (72), the water provided by the water source (71) enters the eluent channel (12) to form the eluent, and the eluent passes through the injector (73), the chromatographic column (74), the suppressor (75), and the detector (76) and enters the regeneration liquid channel (13) to form the regeneration liquid, and then becomes waste liquid after electrolysis and is discharged from the regeneration liquid channel (13).

10. The chromatographic detection device according to claim 8, characterized in that: The chromatographic detection device further comprises a stock solution bottle and a stock solution pump. Under the action of the stock solution pump, the stock solution circulates between the stock solution bottle and the stock solution channel (11), or The raw liquid bottle is directly connected to the raw liquid channel (11).

Images