CN207816918U - A kind of liquid chromatograph for complex sample multi-cycle separation - Google Patents

Abstract

The utility model is related to a kind of liquid chromatographs for complex sample multi-cycle separation, including liquid phase separation access, liquid phase separation access end is connected with several one or six direction changeover valves and intermediate valve group in turn, the intermediate valve group is connect with the head end of liquid phase separation access, constitute multi-cycle separation circuit, it is connected with transfer tube between the intermediate valve group and liquid phase separation access, the intermediate valve group is connected to the solvent bottle for containing mobile phase, collecting pipe is set on one or six direction changeover valve, it will be in the collecting pipe access multi-cycle separation circuit of different six direction changeover valves, it can receive different cycle peaks, realize the separation of complex sample.

Description

A Liquid Chromatography Apparatus for Circular Separation of Complicated Samples

technical field

The utility model relates to the technical field of separation equipment, in particular to a liquid chromatograph used for circular separation of complex samples.

Background technique

High-performance liquid chromatography is the mainstream in the field of analysis and separation science today. It is an important branch of chromatography. It uses liquid as the mobile phase and uses a high-pressure infusion system. The mobile phase is pumped into the chromatographic column equipped with the stationary phase. After the components in the column are separated, they enter the detector for detection, thereby realizing the analysis of the sample. This method has become an important analysis and separation technology in the fields of chemistry, medicine, industry, agronomy, commodity inspection and legal inspection. At the same time, with the rapid development of the field of chromatographic column packing, the column efficiency and separation efficiency have been greatly improved, and it has the advantages of high separation efficiency, good selectivity, high detection sensitivity, automatic operation, and wide application range.

Although high-performance liquid chromatography has many advantages in the separation process, in the analysis and separation of complex samples: such as the complex structure of natural products, it is difficult for conventional high-performance liquid chromatography to analyze and separate many compounds in natural products at one time: including enantiometry The analysis and separation of isomers, diastereomers, isomers or compounds with similar structures and very similar retention times are difficult to be directly analyzed and separated from complex mixed components by the above method. Two-dimensional/multi-dimensional high-performance liquid chromatography analysis and separation are required for the above-mentioned samples. During secondary analysis and separation, the sample is taken out through the pipeline and connected to two-dimensional high-performance liquid chromatography, or the solvent in the column is rebalanced for secondary analysis and separation. For secondary separation, the number of instruments required is large, the operation process is complicated, and the separation effect for multiple complex samples is poor.

Utility model content

In order to overcome the above-mentioned technical defects, the utility model provides a liquid chromatograph for the cyclic separation of complex samples, which can realize the cyclic separation of multi-component complex samples. In order to achieve the above-mentioned purpose, the utility model adopts the following technical scheme:

A liquid chromatograph for complex sample circulation separation, including a liquid phase separation channel, the end of the liquid phase separation channel is connected to a number of first six-way switching valves and intermediate valve groups in sequence, and the intermediate valve group is connected to the liquid phase The head end of the separation passage is connected to form a circulating separation circuit. A driving pump is connected between the intermediate valve group and the liquid phase separation passage. The intermediate valve group is connected with the solvent bottle containing the mobile phase. The driving pump can drive the mobile phase through the The middle valve group enters the liquid phase separation passage, and a collection pipe is arranged between the two connection ports of the first six-way switching valve. The two connection ports of the unconnected collection pipe are used as sample inlet and sample outlet, and two adjacent six-way switching valves The sample outlet of the valve is connected to the sample inlet, and a connecting pipe is set between the remaining two connection ports. The collection pipes of different six-way switching valves are connected to the circulation separation circuit, which can receive different circulation peaks and realize the separation of complex samples.

Further, the intermediate valve group is a second six-way switching valve, one connection port of the second six-way switching valve is in communication with the connection port of the first six-way switching valve as the sample outlet, and one connection port is connected through the drive pump In the liquid phase separation channel, one connection port is used as a sample collection port, one connection port is connected to a solvent bottle containing a mobile phase, and a connection tube is arranged between the remaining two connection ports.

Further, the intermediate valve group is a first three-way valve and a second three-way valve connected in sequence, one connection port of the first three-way valve communicates with the sample outlet of the six-way switching valve, and one connection port is used as a sample collection port. The remaining one connection port communicates with one connection port of the second three-way valve, the other connection port of the second three-way valve is connected to the liquid phase separation passage through the driving pump, and the remaining one connection port of the second three-way valve is connected The port is connected to the solvent bottle containing the mobile phase.

Further, the liquid phase separation path includes a sequentially connected sampling device, a liquid chromatography column, and a detector, the sampling device is used for the sample to enter the separation path, the liquid phase chromatographic column separates the sample, and the detector is used for Samples are tested.

Further, the sampling device is a six-way sampling valve.

The utility model also discloses a working method of a liquid chromatograph used for the cyclic separation of complex samples, which includes the following steps:

Step 1: Switch the first six-way switching valve to the state where the connection port used as the sample inlet is connected to the connection port connected to the collection pipe, connect the driving pump to the connection port of the first six-way switching valve as the sample inlet, and Under the action of the pump, the mobile phase is pumped in, the mobile phase flows through multiple first six-way switching valves in sequence, and flows out from the middle valve group, and the collection pipe is filled with the mobile phase.

Step 2: Switch multiple first six-way valves to the state where the connection port used as the sample inlet is connected to the connection port used as the sample outlet, and the driving pump is connected to the six-way sampling valve and the intermediate valve group. Under the action of the driving pump, , the mobile phase in the solvent bottle flows into the entire circulating separation loop, and finally fills the entire circulating separation loop until the hydrodynamic equilibrium is reached.

Step 3: After reaching the hydrodynamic equilibrium, the sample is dissolved in the mobile phase and then injected into the six-port injection valve for liquid chromatography separation.

Further, in the step 3, for the samples with high resolution, the samples flowing out from the middle valve group are directly collected to realize the one-dimensional liquid chromatography separation of the samples.

Further, in the step 3, for the samples that are difficult to separate by one-dimensional liquid chromatography, the intermediate valve group is adjusted, and the sample flowing out of the detector enters the liquid chromatography column again through the intermediate valve group for separation, so as to realize the cyclic separation of the sample, and the separation The situation is detected by the detector in real time. After the separation is completed, the intermediate valve group is adjusted so that the solvent bottle is connected to the liquid phase separation channel through the intermediate valve group and the driving pump, which is convenient for the next use.

Further, in the step 3, for the separation of multi-component and complex samples, the collection pipes of different first six-way switching valves are connected to the circulation separation circuit, which can receive different circulation peaks, and realize the circulation separation of complex samples. The situation is detected by the detector in real time. After the separation is completed, adjust the intermediate valve group so that the solvent bottle passes through the intermediate valve group and drives the pump to separate from the liquid phase, which is convenient for the next use.

The beneficial effects of the utility model:

1. The liquid chromatograph of the present invention has an intermediate valve group, which can realize the cyclic separation of samples, has good separation effect, is easy to operate, and uses a small number of instruments.

2. With the liquid phase flow chromatograph of the present invention, the separated samples can be collected quickly.

3. In the liquid chromatograph of the present invention, a collection pipe is arranged on the first six-way switching valve, and the collection pipes of different first six-way switching valves are connected to the circulation separation circuit, which can receive different circulation peaks and realize multi-component Separation and collection of complex samples.

Description of drawings

The accompanying drawings constituting a part of the present application are used to provide further understanding of the present application, and the schematic embodiments and descriptions of the present application are used to explain the present application and not to limit the present application.

Fig. 1 is the utility model embodiment 1 solvent equilibrium schematic diagram;

Fig. 2 is a schematic diagram of primary liquid chromatography separation in Example 1 of the utility model;

Fig. 3 is the schematic diagram of circulation separation of the utility model embodiment 1;

Fig. 4 is a schematic diagram of a multi-component complex sample connected to a collection tube in Embodiment 1 of the present utility model;

Fig. 5 is a schematic diagram of the cyclic separation of multi-component complex samples in Example 1 of the present utility model;

Fig. 6 is a schematic diagram of solvent balance in Embodiment 2 of the present utility model;

Fig. 7 is a schematic diagram of primary liquid chromatography separation in Example 2 of the utility model;

Fig. 8 is a schematic diagram of cycle separation in embodiment 2 of the present invention;

Fig. 9 is a schematic diagram of a multi-component complex sample connected to a collection tube in Example 2 of the utility model;

Figure 10 is a schematic diagram of the cyclic separation of multi-component complex samples in Example 2 of the present utility model;

Among them: 1. The first six-way switching valve, 2. Drive pump, 3. Solvent bottle, 4. Collection pipe, 5. Connecting pipe, 6. The second six-way switching valve, 7. Sampling device, 8. Liquid phase Chromatographic column, 9. detector, 10. first three-way valve, 11. second three-way valve.

Detailed ways

It should be pointed out that the following detailed description is exemplary and intended to provide further explanation to the present application. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.

It should be noted that the terminology used here is only for describing specific implementations, and is not intended to limit the exemplary implementations according to the present application. As used herein, unless the context clearly dictates otherwise, the singular is intended to include the plural, and it should also be understood that when the terms "comprising" and/or "comprising" are used in this specification, they mean There are features, steps, operations, means, components and/or combinations thereof.

As introduced in the background technology, the existing liquid chromatograph cannot realize the cyclic separation of samples, and the separation effect for multi-component complex samples is poor. phase chromatograph.

In a typical embodiment 1 of the present application, a liquid chromatograph for cyclic separation of complex samples includes a liquid phase separation path, and the end of the liquid phase separation path is sequentially connected to the first six-way switching valve 1 and the middle A valve group, the middle valve group is connected to the head end of the liquid phase separation passage to form a circulation separation circuit, a drive pump 2 is connected between the middle valve group and the liquid phase separation passage, and the middle valve group is connected to the liquid phase separation passage. The solvent bottle 3 is connected, and the driving pump can drive the mobile phase through the middle valve group to enter the liquid phase separation channel. A collection pipe 4 is set between the connection port I and the connection port II of the first six-way switching valve, and the connection port III is used as the sample inlet. , the connection port IV is used as the sample outlet, and the connection pipe 5 is set between the connection port V and the connection port VI, and the collection pipe of the first six-way switching valve is connected to the circulation separation circuit to realize the separation of specific components in the sample.

The middle valve group is a second six-way switching valve 6, the connection port II of the second six-way switching valve is in communication with the connection port IV of the first six-way switching valve as the sample outlet, and the connection port I is connected through the driving pump. The liquid phase separation channel, the connection port V is used as the sample collection port, the connection port VI is connected with the solvent bottle containing the mobile phase, and the connection tube is set between the connection port III and the connection port IV.

The liquid phase separation path comprises a sequentially connected sampling device 7, a liquid chromatography column 8 and a detector 9, the sampling device is used for the sample to enter the separation path, the liquid phase chromatographic column separates the sample, and the detector is used for detecting The sample is tested, and the sampling device is a six-way sampling valve.

The utility model also discloses a working method of a liquid chromatograph used for the cyclic separation of complex samples, which includes the following steps:

Step 1: Switch the first six-way switching valve to the state where the connection port III is connected to the connection port II, connect the driving pump to the connection port III of the first six-way switching valve, and pump the mobile phase under the action of the driving pump , the mobile phase flows through the first six-way switching valve in turn, and flows out from the connection port V of the circulating six-way valve, and the collection pipe is filled with mobile phase.

The specific flow direction of the mobile phase in the first six-way switching valve is connection port III→connection port II→connection port I→connection port VI→connecting pipe→connection port V→connection port IV, and flows out through the first six-way switching valve Then it enters the circulation six-way valve through the connection port II of the circulation six-way valve, and the specific flow direction in the second six-way switching valve is: connection port II→connection port III→connecting pipe→connection port IV→connection port V.

Step 2: As shown in Figure 1, switch the multiple first six-way valves to the state where the connection port III is connected to the connection port IV, and drive the pump to connect with the connection port I of the six-way sampling valve and the second six-way switching valve , under the action of the driving pump, the mobile phase in the solvent bottle flows into the entire circulation separation loop, and finally fills the entire circulation separation loop until the hydrodynamic equilibrium is reached.

The specific flow direction of the mobile phase is: solvent bottle→second six-way switching valve (Ⅵ→Ⅰ)→six-way sampling valve→liquid chromatography column→detector→first six-way switching valve (Ⅲ→Ⅳ)→second Six-way switching valve (Ⅱ→Ⅲ→Ⅳ→Ⅴ)

Step 3: After reaching the hydrodynamic equilibrium, the sample is dissolved in the mobile phase and then injected into the six-port injection valve for liquid chromatography separation.

As shown in Figure 2, for samples with high resolution, the samples flowing out of the connection port V of the second six-way switching valve are directly collected to realize the one-dimensional liquid chromatography separation of the samples.

As shown in Figure 3, for samples that are difficult to separate by one-dimensional liquid chromatography, adjust the second six-way switching valve so that the connection port II of the second six-way switching valve communicates with connection port I, and the sample flowing out of the detector passes through the first The six-way switching valve and the second six-way switching valve enter the liquid chromatographic column again for separation to realize the cyclic separation of samples. The separation is detected in real time by the detector. After the separation is completed, adjust the connection port II and The connection port III is connected, so that the solvent bottle is connected to the liquid phase separation channel through the second six-way switching valve and the driving pump, which is convenient for the next use.

As shown in Figure 4-5, for the separation of multi-component complex samples, the collection pipe of the first six-way switching valve is connected to the circulation separation circuit, which can receive the circulation peak of specific components and realize the circulation separation of complex samples. , connect the connection port III of the first switching six-way valve to the connection port II, the sample enters the collection pipe through connection port III and connection port II, and flows out of the collection pipe into the second six-way switching valve, adjust the second six-way switching valve , connect the circulation loop, and then carry out circulation separation. The separation is detected in real time by the detector. After the separation is completed, adjust the second six-way switching valve so that the solvent bottle is connected to the liquid phase separation channel through the second six-way switching valve and the drive pump. , Adjust the first six-way switching valve, and the collection pipe is not connected to the circulation separation circuit, which is convenient for the next use.

Multiple first six-way switching valves can be set according to the sample situation, and the collection pipes of different first six-way switching valves can be connected to the circulation separation circuit, which can receive the circulation peaks of different components and realize the separation of multi-component complex samples.

Because the sample components to be collected may not completely fill the collection tube, when switching separation, air bubbles will enter the countercurrent chromatography, thereby affecting the separation, so the collection tube is pre-filled with mobile phase to ensure the elimination of air bubbles.

In another embodiment of the present application, as shown in Figure 6-10, the intermediate valve group adopts the first three-way valve 10 and the second three-way valve 11 connected in sequence, and the first three-way valve has a connection port I and The connection port IV of the six-way switching valve as the sample outlet is connected, one connection port III is used as the sample collection port, and the remaining connection port II is connected to one connection port I of the second three-way valve, and the other connection port of the second three-way valve is One connection port II is connected to the liquid phase separation channel through the drive pump, and the remaining connection port III of the second three-way valve is connected to the solvent bottle containing the mobile phase.

The method of use is roughly the same as that in the example, the difference is that when the solvent is balanced, the mobile phase flows out from the connection port III of the first three-way valve, and when performing one-dimensional liquid phase separation, connect the connection port I of the first three-way valve with the connection port Ⅲ is connected, use the connection port Ⅲ of the first three-way valve to collect samples, and when performing circulation separation, connect the connection port Ⅰ and connection port Ⅲ of the second three-way valve to connect the circulation separation circuit.

Although the specific implementation of the utility model has been described above in conjunction with the accompanying drawings, it does not limit the protection scope of the utility model. Those skilled in the art should understand that on the basis of the technical solution of the utility model, those skilled in the art do not need to Various modifications or deformations that can be made with creative efforts are still within the protection scope of the present utility model.

Claims (5)

1. A liquid chromatograph for complex sample circulation separation, characterized in that it comprises a liquid phase separation path, and the end of the liquid phase separation path is connected with a number of first six-way switching valves and intermediate valve groups in sequence, the The intermediate valve group is connected with the head end of the liquid phase separation channel to form a circulating separation circuit. A driving pump is connected between the intermediate valve group and the liquid phase separation channel. The intermediate valve group communicates with the solvent bottle containing the mobile phase to drive The pump can drive the mobile phase to enter the liquid phase separation channel through the middle valve group. A collection pipe is arranged between the two connection ports of the first six-way switching valve. The two connection ports of the unconnected collection pipe are used as sample inlet and sample outlet. The sample outlets of two adjacent six-way switching valves are connected to the sample inlet, and connecting pipes are set between the remaining two connection ports. The collection pipes of different six-way switching valves are connected to the circulation separation circuit, which can receive different circulation peaks and realize Separation of complex samples. 2. A kind of liquid chromatograph that is used for complex sample circulation separation as claimed in claim 1, is characterized in that, described intermediate valve group is a second six-way switching valve, and described second six-way switching valve is a The connection port is connected with the first six-way switching valve as the connection port of the sample outlet, one connection port is connected to the liquid phase separation channel through the drive pump, one connection port is used as the sample collection port, and one connection port is connected with the solvent bottle containing the mobile phase, and the remaining A connecting pipe is arranged between the two connecting ports. 3. A kind of liquid chromatograph that is used for complex sample circulation separation as claimed in claim 1, is characterized in that, described intermediate valve group is the first three-way valve and the second three-way valve that are connected successively, and described One connection port of the first three-way valve communicates with the sample outlet of the six-way switching valve, one connection port serves as a sample collection port, and the remaining one connection port communicates with a connection port of the second three-way valve, and the second three-way valve’s The other connection port is connected to the liquid phase separation channel through the drive pump, and the remaining connection port of the second three-way valve is connected to the solvent bottle containing the mobile phase. 4. a kind of liquid chromatograph that is used for the circulation separation of complex sample as claimed in claim 1, is characterized in that, described liquid phase separation path comprises the sampling device, liquid phase chromatographic column and detector that are connected successively, and The sampling device is used for the sample to enter the separation channel, the liquid chromatography column separates the sample, and the detector is used for detecting the sample. 5. A liquid chromatograph for complex sample circulation separation as claimed in claim 4, wherein said sampling device is a six-way sampling valve.