CN115219606A - Water sample automatic pretreatment device, treatment method and water sample automatic detection system - Google Patents

Abstract

The invention discloses a water sample automatic pretreatment device, a treatment method and a water sample automatic detection system. The water sample automatic pretreatment device includes a rack and a solid-phase microextraction mechanism, a liquid sampling mechanism, a nitrogen blowing mechanism, a liner grabbing mechanism, a solvent supply mechanism, a vortex mixing mechanism, an automatic A liner changing mechanism, an incubation mechanism, an aging mechanism, and a multi-directional movement mechanism; the solid-phase micro-extraction mechanism has a solid-phase micro-extraction extraction head for absorbing organic matter in the sample; the liquid sampling mechanism has a Liquid syringe for adding liquid sample. The water sample automatic pretreatment device of the present invention can automatically complete two pretreatment modes of headspace solid-phase microextraction and liquid-liquid extraction for water samples, and the treated water samples can be automatically injected into a chromatograph for detection and analysis, with simple operation and detection. High efficiency, operator health and environment friendly.

Description

Water sample automatic pretreatment device, treatment method and water sample automatic detection system

technical field

The invention relates to the field of detection, in particular to a water sample automatic pretreatment device, a processing method and a water sample automatic detection system.

Background technique

With the rapid development of industry, a large number of various types of organic pollutants are discharged into the water environment with human activities. These organic pollutants have the characteristics of many types, low content, complex composition and great harm, which seriously threaten the safety of water resources. . In order to understand the status of water pollution, it is necessary to detect the composition of organic matter in the water through various technical means, and then trace the source of pollutants in the water environment, so as to realize the source control of the pollution source and improve the water quality of the target water body.

Organic compounds in water can be divided into volatile organic compounds (VOCs), semi-volatile organic compounds (SVOCs) and non-volatile organic compounds according to their physical properties. Among them, volatile organic compounds are compounds with a boiling point below 170 °C, mainly including halogenated hydrocarbons, benzene series, etc.; semi-volatile and non-volatile organic compounds have a boiling point above 170 °C, and the main compounds include polycyclic aromatic hydrocarbons, organic pesticides, chlorinated compounds, etc. Benzene, nitrobenzene, aniline, etc.

Volatile organic compounds in water are often extracted from water by headspace (HS) injection method and then detected and analyzed by gas chromatography. Semi-volatile organic compounds and non-volatile organic compounds are generally extracted from water samples by liquid-liquid extraction and then detected and analyzed by gas chromatography. The above two detection and analysis methods have the following shortcomings: 1) The organic pollutants in the water are usually mixed pollution of multiple different types of organic substances. In order to have a comprehensive understanding of the sources of the water pollutants, headspace gas chromatography and liquid Liquid extraction gas chromatography is used in combination, but the two pretreatment methods of headspace sampling and liquid-liquid extraction in the prior art can only be separately processed and then analyzed by gas chromatography, which requires the use of various types of equipment. 2) In addition, headspace sampling generally can only extract part of the gas at the top of the headspace bottle (usually 1mL) and inject it into the chromatograph for analysis. The sample utilization rate is low, making it difficult to detect some trace components. 3) The organic content in the water is relatively low. The conventional liquid-liquid extraction method needs to use a large amount of water samples (above 250 mL) and add tens to hundreds of milliliters of organic solvents for extraction in a separatory funnel, and then extract The organic phase is dried with anhydrous sodium sulfate and then concentrated and enriched with a rotary evaporator or nitrogen blower to meet the detection sensitivity requirements. The whole process consumes a lot of samples and organic solvents. Moreover, the detection and analysis methods in the prior art can only use manual methods or use an extractor to achieve semi-automatic liquid-liquid extraction. After the processing is completed, it needs to be manually transferred to a chromatograph for sample injection detection and analysis, which is cumbersome and time-consuming. In addition, the whole process of liquid-liquid extraction requires the use of a large amount of harmful organic solvents, and the existing technology requires more manual operations, which will cause certain harm to the health of operators and the environment.

SUMMARY OF THE INVENTION

Based on this, it is necessary to provide an automatic water sample pretreatment device, a treatment method and an automatic water sample detection system. The water sample automatic pretreatment device of the present invention can automatically complete two pretreatment methods of headspace solid-phase microextraction and liquid-liquid extraction for water samples, and the treated water samples can be automatically injected into a chromatograph for detection and analysis, with simple operation and detection. High efficiency, operator health and environment friendly.

An automatic pretreatment device for water samples, comprising a rack and a solid-phase microextraction mechanism, a liquid sampling mechanism, a nitrogen blowing mechanism, a liner grabbing mechanism, a solvent supply mechanism, and a vortex mixing mechanism mounted on the rack. mechanism, incubation mechanism, aging mechanism, and multi-directional motion mechanism; the solid-phase micro-extraction mechanism has a solid-phase micro-extraction extraction head for adsorbing organic matter in the sample; the liquid sampling mechanism has a liquid sample for sucking and adding liquid samples. The nitrogen blowing mechanism is used for sample nitrogen blowing and concentration; the liner grabbing mechanism is used for grabbing and moving the liner; the solvent supply mechanism is used for providing extraction solvent; the vortex mixer The homogenization mechanism is used for vortex mixing of the sample; the incubation mechanism is used for incubating the sample; the aging mechanism is used for aging the extraction head of the solid-phase microextraction; the multi-directional motion mechanism can automatically obtain the solid-phase microextraction head. Extraction mechanism, the liquid sampling mechanism, the nitrogen blowing mechanism or the liner grabbing mechanism and drive it to move.

In one embodiment, the water sample automatic pretreatment device further comprises a tool holder, the tool holder is arranged on the frame, the liquid sampling mechanism, the nitrogen blowing mechanism and the liner grabbing mechanism mounted on the tool holder.

In one embodiment, the water sample automatic pre-processing device further includes a liner rack, and the liner rack is used for placing the liner.

In one embodiment, the water sample automatic pre-processing device further includes a sample holder, the sample holder is provided with a plurality of placement positions for placing the sample bottles, and each of the placement positions is respectively marked with a position serial number.

In one embodiment, the incubation mechanism includes one or more of a heating part, an oscillating part and an ultrasonic part.

A water sample automatic detection system, comprising a chromatograph and the water sample automatic pretreatment device, the water sample automatic pretreatment device can cooperate with the injection port of the chromatograph, and the water sample automatic pretreatment device After the sample is processed, the sample is placed in the liner to be concentrated by nitrogen blowing, and then the liner is grabbed by the liner grabbing mechanism and put into the injection port of the chromatograph for analytical injection.

In one embodiment, the chromatograph includes, but is not limited to, gas chromatography, gas chromatography-mass spectrometry, gas chromatography-triple quadrupole mass spectrometry, and comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry instrument.

A water sample automatic pretreatment method using the described water sample automatic pretreatment device, comprising the following steps:

When performing the automatic headspace solid phase microextraction mode, the following steps are included:

S1: Add a predetermined amount of water sample to be analyzed into the sample bottle;

S2: Control the multi-directional motion mechanism to obtain the solid-phase micro-extraction mechanism, control the multi-directional motion mechanism to drive the solid-phase micro-extraction mechanism to move the sample vial to the incubation mechanism, and incubate the sample vial in the incubation mechanism according to the preset incubation conditions to realize the volatilization to be analyzed. volatile organic compounds in water samples;

S3: Control the multi-directional motion mechanism to drive the solid-phase microextraction mechanism to move to the aging mechanism, and place the extraction head on the solid-phase microextraction mechanism into the aging mechanism for aging treatment to remove residual volatile organic compounds;

S4: After the sample incubation is completed, the multi-directional motion mechanism is controlled to drive the solid-phase micro-extraction mechanism to move to the incubation mechanism, and the extraction head on the solid-phase micro-extraction mechanism is placed in the sample bottle, and the sample bottle is extracted under preset extraction conditions. volatile organics at the top;

S5: After the extraction is completed, the multi-directional motion mechanism is controlled to drive the solid-phase micro-extraction mechanism to move to the chromatographic injection port of the chromatograph, and the extraction head is placed in the chromatographic injection port for sample analysis for the chromatograph to detect and analyze;

When the automatic liquid-liquid extraction mode is performed, the following steps are included:

s1: add a predetermined amount of water sample to be analyzed into the first sample bottle; add a predetermined amount of desiccant into the second sample bottle; take the first liner for use;

s2: control the multi-directional movement mechanism to obtain the liquid sampling mechanism, and control the multi-directional movement mechanism to drive the liquid sampling mechanism to move to the solvent supply mechanism to extract a predetermined amount of extraction solvent and inject it into the first sample bottle;

s3: control the multi-directional motion mechanism to drive the liquid sampling mechanism to move the first sample bottle and move it into the vortex oscillation mechanism for vortex mixing, and let it stand for a predetermined time to extract the organic matter in the water sample to be analyzed;

s4: Control the multi-directional movement mechanism to drive the liquid sampling mechanism to absorb the layered supernatant in the first sample bottle and transfer it to the second sample bottle, and control the multi-directional movement mechanism to drive the liquid sampling mechanism to move the second sample bottle Vortex mixing in the vortex shaking mechanism to dry and remove water;

s5: control the multi-directional motion mechanism to drive the liquid sampling mechanism to extract a predetermined amount of liquid from the second sample bottle and add it to the first liner;

s6: Control the multi-directional motion mechanism to release the liquid sampling mechanism and obtain the nitrogen blowing mechanism, control the multi-directional motion mechanism to drive the nitrogen blowing mechanism to move into the first liner, and perform nitrogen blowing on the liquid in the first liner to remove the solvent and realize the sample concentrated enrichment;

s7: Control the multi-directional motion mechanism to release the nitrogen blowing mechanism and obtain the liner grabbing mechanism, control the multi-directional motion mechanism to drive the liner grabbing mechanism to move to the chromatographic injection port of the chromatograph, and control the multi-directional motion mechanism to drive the liner grabber The taking mechanism moves the first liner into the injection port of the chromatograph for detection and analysis by the chromatograph.

In one embodiment, a predetermined amount of filler is added to the spare first liner, and the filler includes glass wool or an adsorbent.

In one embodiment, when the automatic headspace solid-phase microextraction mode is performed, a predetermined amount of sodium chloride is also added to the sample bottle when the predetermined amount of the water sample to be analyzed is added;

And/or, when the automatic liquid-liquid extraction mode is performed, a predetermined amount of a demulsifier is also added at the same time when a predetermined amount of the water sample to be analyzed is added to the first sample bottle.

In one of the embodiments, the automatic headspace solid-phase microextraction mode and the automatic liquid-liquid extraction mode are controlled to automatically switch between two modes, so that the water samples are automatically pretreated in different ways to realize the detection of different types of targets, and the automatic The switching process is as follows:

The steps of performing the automatic headspace solid-phase microextraction mode are saved as a first method file, and the automatic liquid-liquid extraction mode is saved as a second method file;

A running sequence table is set in the automatic water sample pretreatment device, and the position serial number of the sample rack where each sample bottle is located and the first method file or second method file corresponding to the sample bottle are filled in the running sequence table, and the The water sample automatic pre-processing device sequentially loads the first method file or the second method file corresponding to each sample to process the samples in the sample bottle at the corresponding position according to the running sequence table.

The above-mentioned automatic pretreatment device for water samples can automatically complete two pretreatment methods of headspace solid-phase microextraction and liquid-liquid extraction for water samples, and the treated water samples can be automatically injected into a chromatograph for detection and analysis, with simple operation and high detection efficiency. High, operator health and environment friendly.

Compared with the traditional pretreatment method, the above-mentioned automatic pretreatment device for water samples has the following beneficial effects:

(1) compared with the traditional water sample liquid-liquid extraction method, it often needs to consume hundreds of milliliters of samples and several tens of milliliters of organic solvents, and the present invention only needs to use about ten milliliters of samples and several milliliters of organic solvents for sample extraction, Significantly reduces sample loading and solvent consumption.

(2) Compared with the conventional liquid-liquid extraction, it is necessary to transfer the extraction solvent to the flask and use nitrogen blowing or rotary evaporation to concentrate and enrich the sample to about 200 μL, and then use a micro syringe to inject 1 μL into the chromatograph for analysis. The utilization rate is low; in the present invention, nitrogen blowing and concentration is performed in the liner, and all the concentrated samples are injected into the chromatograph for analysis, thereby effectively improving the utilization rate of the samples.

(3) Liquid-liquid extraction can be carried out automatically, reducing manual participation, improving accuracy, and reducing human pollution introduced in the operation process.

(4) The present invention adopts the combination of automatic liquid-liquid extraction and solid-phase micro-extraction, the two modes can be automatically switched, and can realize the automatic pretreatment of different types of organic substances in the water sample to be analyzed.

(5) The present invention can realize the automatic injection of the pre-treated sample into the chromatograph for analysis, and realize the automatic detection of the organic matter in the water.

(6) The water sample automatic pretreatment device has a wide range of applications, and the equipment used for sample detection is a chromatograph, including but not limited to the following types: gas chromatography (GC), gas chromatography-mass spectrometry (GCMS), gas chromatography Chromatography-triple quadrupole mass spectrometry (GC-MSMS), comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry (GC×GC-TOFMS).

(7) The water sample automatic pretreatment device of the present invention is applicable to a wide range of treatment objects, including but not limited to surface water, groundwater, drinking water and seawater.

Description of drawings

FIG. 1 is a schematic diagram of an automatic pre-processing device according to an embodiment of the present invention.

Description of reference numerals

10. Automatic pretreatment device; 100, rack; 200, solid-phase microextraction mechanism; 300, liquid sampling mechanism; 400, nitrogen blowing mechanism; 500, tool holder; 600, solvent supply mechanism; 700, vortex mixing mechanism; 800, incubation mechanism; 900, aging mechanism; 1000, multi-directional movement mechanism; 1100, sample rack; 1200, liner rack.

Detailed ways

In order to make the above objects, features and advantages of the present invention more clearly understood, the specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. However, the present invention can be implemented in many other ways different from those described herein, and those skilled in the art can make similar improvements without departing from the connotation of the present invention. Therefore, the present invention is not limited by the specific embodiments disclosed below.

In the description of the present invention, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", " Back, Left, Right, Vertical, Horizontal, Top, Bottom, Inner, Outer, Clockwise, Counterclockwise, Axial , "radial", "circumferential" and other indicated orientations or positional relationships are based on the orientations or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying the indicated device or Elements must have a particular orientation, be constructed and operate in a particular orientation and are therefore not to be construed as limitations of the invention.

In addition, the terms "first" and "second" are only used for descriptive purposes, and should not be construed as indicating or implying relative importance or implying the number of indicated technical features. Thus, a feature delimited with "first", "second" may expressly or implicitly include at least one of that feature. In the description of the present invention, "plurality" means at least two, such as two, three, etc., unless otherwise expressly and specifically defined.

In the present invention, unless otherwise expressly specified and limited, the terms "installed", "connected", "connected", "fixed" and other terms should be understood in a broad sense, for example, it may be a fixed connection or a detachable connection , or integrated; it can be a mechanical connection or an electrical connection; it can be directly connected or indirectly connected through an intermediate medium, it can be the internal connection of two elements or the interaction relationship between the two elements, unless otherwise specified limit. For those of ordinary skill in the art, the specific meanings of the above terms in the present invention can be understood according to specific situations.

In the present invention, unless otherwise expressly specified and limited, a first feature "on" or "under" a second feature may be in direct contact between the first and second features, or the first and second features indirectly through an intermediary touch. Also, the first feature being "above", "over" and "above" the second feature may mean that the first feature is directly above or obliquely above the second feature, or simply means that the first feature is level higher than the second feature. The first feature being "below", "below" and "below" the second feature may mean that the first feature is directly or obliquely below the second feature, or simply means that the first feature has a lower level than the second feature.

It should be noted that when an element is referred to as being "fixed to" or "disposed on" another element, it can be directly on the other element or an intervening element may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present. The terms "vertical", "horizontal", "upper", "lower", "left", "right" and similar expressions used herein are for the purpose of illustration only and do not represent the only embodiment.

Unless otherwise defined, 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 invention belongs. The terms used herein in the description of the present invention are for the purpose of describing specific embodiments only, and are not intended to limit the present invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

Referring to FIG. 1 , an embodiment of the present invention provides an automatic pretreatment device 10 for water samples.

A water sample automatic pretreatment device 10, comprising a rack 100 and a solid-phase microextraction mechanism 200, a liquid sampling mechanism 300, a nitrogen blowing mechanism 400, a liner grabbing mechanism, and a solvent supply mechanism 600 mounted on the rack 100. , Vortex mixing mechanism 700, incubation mechanism 800, aging mechanism 900, multi-directional movement mechanism 1000.

The solid phase microextraction mechanism 200 has a solid phase microextraction extraction head for adsorbing organic matter in the sample.

The liquid sampling mechanism 300 has a liquid sampling needle for aspirating and adding a liquid sample.

The nitrogen blowing mechanism 400 is used for nitrogen blowing and concentration of the sample.

The liner grab mechanism is used to grab and move the liner. The liner gripping mechanism is not shown in the drawings. The liner gripping mechanism may be an electric gripper.

The solvent supply mechanism 600 is used to supply the extraction solvent.

The vortex mixer 700 is used to vortex the sample.

Incubation mechanism 800 is used for incubating samples.

The aging mechanism 900 is used for the aging of the SPE extraction head.

Referring to FIG. 1 , the multi-directional motion mechanism 1000 can automatically acquire and drive the solid phase microextraction mechanism 200 , the liquid sampling mechanism 300 , the nitrogen blowing mechanism 400 or the liner grasping mechanism to move. The multidirectional motion mechanism 1000 can move in the X, Y, and Z directions.

Preferably, in one embodiment, the multi-directional motion mechanism 1000 may be a manipulator.

In a specific example, as shown in FIG. 1 , the water sample automatic pretreatment device 10 further includes a tool holder 500 . The tool holder 500 is arranged on the rack 100 , and the liquid sampling mechanism 300 , the nitrogen blowing mechanism 400 and the liner grabbing mechanism are mounted on the tool holder 500 . The tool holder 500 is provided with three workstations, and the three workstations are respectively used for placing the liquid sampling mechanism 300 , the nitrogen blowing mechanism 400 and the liner grabbing mechanism.

The liquid sampling mechanism 300 , the nitrogen blowing mechanism 400 and the liner grabbing mechanism can be set separately, or one or more of them can be integrated into an integrated mode, that is, one mechanism can simultaneously display the sampling, nitrogen blowing and the ability to grab.

In a specific example, as shown in FIG. 1 , the water sample automatic pretreatment device 10 further includes a liner holder 1200 . The liner rack 1200 is mounted on the frame 100 . The liner rack 1200 is used to place the liner.

In a specific example, as shown in FIG. 1 , the water sample automatic pretreatment device 10 further includes a sample holder 1100 . The sample rack 1100 is mounted on the rack 100 . The sample rack 1100 is provided with a plurality of placement positions for placing sample vials, and each placement position is marked with a position serial number respectively.

In a specific example, the incubation mechanism 800 includes one or more of a heating part, an oscillating part and an ultrasonic part. For example, in one embodiment, the incubation mechanism 800 includes a heating component, in another embodiment, the incubation mechanism 800 includes an oscillating component, and in another embodiment, the incubation mechanism 800 includes an ultrasonic component. Further, the incubation mechanism 800 may include a heating part, an oscillating part and an ultrasonic part at the same time.

In a specific example, the liquid sampling mechanism 300 , the nitrogen blowing mechanism 400 and the liner grabbing mechanism of the water sample automatic pretreatment device 10 can be made into two-in-one or three-in-one tools.

In a specific example, the solid-phase microextraction mechanism 200 can be replaced with a headspace sampling tool or a dynamic headspace sampling tool.

The above-mentioned automatic pretreatment device 10 for water samples can automatically complete two pretreatment methods of headspace solid-phase microextraction and liquid-liquid extraction for water samples, and the treated water samples can be automatically injected into a chromatograph for detection and analysis, which is simple to operate and detect. High efficiency, operator health and environment friendly.

An embodiment of the present invention also provides an automatic detection system for water samples.

A water sample automatic detection system, comprising a chromatograph and the above-mentioned water sample automatic pretreatment device 10, the water sample automatic pretreatment device 10 can cooperate with the injection port of the chromatograph, and the water sample automatic pretreatment device 10 processes the sample. Afterwards, the sample was placed in the liner to be concentrated by nitrogen blowing, and then the liner was grabbed by the liner grabbing mechanism and put into the injection port of the chromatograph for analytical injection.

In a specific example, chromatographs include, but are not limited to, gas chromatography (GC), gas chromatography-mass spectrometry (GCMS), gas chromatography-triple quadrupole mass spectrometry (GC-MSMS), and full two-dimensional Gas chromatography-time-of-flight mass spectrometry (GC×GC-TOFMS).

An embodiment of the present invention also provides an automatic pretreatment method for water samples.

A water sample automatic pretreatment method, which uses the above-mentioned water sample automatic pretreatment device, comprising the following steps:

When performing the automatic headspace solid phase microextraction mode, the following steps are included:

S1: Referring to Figure 1, add a predetermined amount of water sample to be analyzed into the sample bottle, tighten the bottle cap, and place the sample bottle on the sample rack 1100.

S2: Control the multi-directional motion mechanism 1000 to obtain the solid-phase micro-extraction mechanism 200, control the multi-directional motion mechanism 1000 to drive the solid-phase micro-extraction mechanism 200 to move the sample vial to the incubation mechanism 800, and incubate the sample vial in the incubation mechanism 800 according to preset incubation conditions , to achieve volatilization of volatile organic compounds in the water sample to be analyzed.

S3: Control the multi-directional motion mechanism 1000 to drive the solid phase microextraction mechanism 200 to move to the aging mechanism 900 and place the extraction head on the solid phase microextraction mechanism 200 into the aging mechanism 900 for aging treatment to remove residual volatile organic compounds.

S4: After the sample incubation is completed, the multi-directional movement mechanism 1000 is controlled to drive the solid-phase micro-extraction mechanism 200 to move to the incubation mechanism 800, and the extraction head on the solid-phase micro-extraction mechanism 200 is placed in the sample bottle. Under preset extraction conditions Extract volatile organics from the top inside the vial.

S5: After the extraction is completed, the multi-directional motion mechanism 1000 is controlled to drive the solid-phase microextraction mechanism 200 to move to the chromatographic injection port of the chromatograph, and the extraction head is placed in the chromatographic injection port for sample analysis for the chromatograph to detect and analyze.

When the automatic liquid-liquid extraction mode is performed, the following steps are included:

s1: Referring to Figure 1, add a predetermined amount of water sample to be analyzed into the first sample bottle on the sample bottle rack, and tighten the bottle cap; add a predetermined amount of dry water to the second sample bottle on the sample bottle rack Take the first liner and place it on the liner rack 1200 for standby use; the desiccant can be anhydrous sodium sulfate, it is not difficult to understand, the desiccant can also be other substances, such as calcium oxide, calcium sulfate, potassium carbonate , anhydrous copper sulfate and potassium hydroxide, etc.

s2: Control the multi-directional motion mechanism 1000 to obtain the liquid sampling mechanism 300, and control the multi-directional motion mechanism 1000 to drive the liquid sampling mechanism 300 to move to the solvent supply mechanism 600 to extract a predetermined amount of extraction solvent and inject it into the first sample bottle.

s3: Control the multi-directional motion mechanism 1000 to drive the liquid sampling mechanism 300 to move the first sample bottle into the vortex oscillating mechanism for vortex mixing, and let it stand for a predetermined time to extract the organic matter in the water sample to be analyzed.

s4: Control the multi-directional motion mechanism 1000 to drive the liquid sampling mechanism 300 to absorb the layered supernatant in the first sample bottle and transfer it to the second sample bottle, and control the multi-directional motion mechanism 1000 to drive the liquid sampling mechanism 300 to move The second sample vial was vortexed into the vortexing mechanism to dry and remove water.

s5: Control the multi-directional motion mechanism 1000 to drive the liquid sampling mechanism 300 to extract a predetermined amount of liquid from the second sample bottle and add it to the first liner.

s6: Control the multi-directional motion mechanism 1000 to release the liquid sampling mechanism 300 and acquire the nitrogen blowing mechanism 400, control the multi-directional motion mechanism 1000 to drive the nitrogen blowing mechanism 400 to move into the first liner, and perform nitrogen blowing on the liquid in the first liner The solvent is removed to achieve sample concentration and enrichment.

s7: Control the multi-directional motion mechanism 1000 to release the nitrogen blowing mechanism 400 and obtain the liner grabbing mechanism, and control the multi-directional motion mechanism 1000 to drive the liner grab mechanism to grab the chromatographic injection port of the chromatograph. and place the empty second liner on the liner rack 1000. The multi-directional motion mechanism 1000 is controlled to drive the liner grabbing mechanism to move to the chromatographic injection port of the chromatograph, and the multi-directional motion mechanism 1000 is controlled to drive the liner grab mechanism to move the first liner to the chromatograph injection port for the chromatograph. Perform detection analysis.

In a specific example, a predetermined amount of filler is added to the spare first liner, and the filler includes glass wool or an adsorbent.

In a specific example, when the automatic headspace solid-phase microextraction mode is performed, a predetermined amount of sodium chloride is also added to the sample bottle when a predetermined amount of the water sample to be analyzed is added. In automatic headspace solid phase extraction, a certain amount of sodium chloride is added to the sample bottle, and the salting out effect is beneficial to the volatilization of organic matter to improve the sensitivity. It is not difficult to understand. Other salts can also be used to replace sodium chloride or not add sodium chloride .

In a specific example, when the automatic liquid-liquid extraction mode is performed, a predetermined amount of water sample to be analyzed is added to the first sample bottle, and a predetermined amount of demulsifier is also added at the same time, and the demulsifier includes sodium chloride. During liquid-liquid extraction, a certain amount of sodium chloride is added to the first sample bottle as a demulsifier, which is beneficial to the stratification of the organic phase and the aqueous phase. If the emulsification of the clean water sample to be analyzed is not serious, sodium chloride may not be added, or other compounds can be used as demulsifiers, or other methods such as ultrasonic vibration can be used for demulsification.

In a specific example, when the automatic headspace solid-phase microextraction mode is performed, the aging mechanism 900 may be used to age the extraction head, and the chromatographic injection port may also be used to age the extraction head.

In one embodiment, the automatic headspace solid-phase microextraction mode and the automatic liquid-liquid extraction mode are controlled to automatically switch, so as to automatically perform different pretreatments on the water sample to realize the detection of different types of targets, and the automatic switching The process is as follows:

The steps of performing the automatic headspace solid-phase microextraction mode are saved as the first method file, and the automatic liquid-liquid extraction mode is saved as the second method file;

A running sequence table is set in the water sample automatic pre-processing device 10, and the position serial number of the sample rack where each sample bottle is located and the first method file or the second method file corresponding to the sample bottle are filled in the running sequence table. The pre-processing device sequentially loads the first method file or the second method file corresponding to each sample to process the samples in the sample bottle at the corresponding position according to the running sequence table.

Compared with the traditional pretreatment method, the above-mentioned automatic pretreatment device 10 for water samples has the following beneficial effects:

(1) compared with the traditional water sample liquid-liquid extraction method, it often needs to consume hundreds of milliliters of samples and several tens of milliliters of organic solvents, and the present invention only needs to use about ten milliliters of samples and several milliliters of organic solvents for sample extraction, Significantly reduces sample loading and solvent consumption.

(2) Compared with the conventional liquid-liquid extraction, it is necessary to transfer the extraction solvent to the flask and use nitrogen blowing or rotary evaporation to concentrate and enrich the sample to about 200 μL, and then use a micro syringe to inject 1 μL into the chromatograph for analysis. The utilization rate is low; in the present invention, nitrogen blowing and concentration is performed in the liner, and all the concentrated samples are injected into the chromatograph for analysis, thereby effectively improving the utilization rate of the samples.

(3) Liquid-liquid extraction can be carried out automatically, reducing manual participation, improving accuracy, and reducing human pollution introduced in the operation process.

(4) The present invention adopts the combination of automatic liquid-liquid extraction and solid-phase micro-extraction, the two modes can be automatically switched, and can realize the automatic pretreatment of different types of organic substances in the water sample to be analyzed.

(5) The present invention can realize the automatic injection of the pre-treated sample into the chromatograph for analysis, and realize the automatic detection of the organic matter in the water.

(6) The water sample automatic pretreatment device 10 has a wide range of applications, and the equipment used for sample detection is a chromatograph, including but not limited to the following types: gas chromatography (GC), gas chromatography-mass spectrometry (GCMS), Gas chromatography-triple quadrupole mass spectrometry (GC-MSMS), comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry (GC×GC-TOFMS).

(7) The water sample automatic pretreatment device 10 of the present invention is applicable to a wide range of treatment objects, including but not limited to surface water, groundwater, drinking water and seawater.

The technical features of the above-described embodiments can be combined arbitrarily. For the sake of brevity, all possible combinations of the technical features in the above-described embodiments are not described. However, as long as there is no contradiction between the combinations of these technical features, All should be regarded as the scope described in this specification.

The above-mentioned embodiments only represent several embodiments of the present invention, and the descriptions thereof are specific and detailed, but should not be construed as a limitation on the scope of the patent of the present invention. It should be pointed out that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can also be made, which all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the appended claims.

Claims (11)

1. a water sample automatic pretreatment device, is characterized in that, comprises rack and solid-phase microextraction mechanism, liquid sampling mechanism, nitrogen blowing mechanism, liner grabbing mechanism, solvent supply that are installed on described rack mechanism, vortex mixing mechanism, incubation mechanism, aging mechanism, and multi-directional motion mechanism; the solid-phase microextraction mechanism has a solid-phase microextraction extraction head for adsorbing organic matter in the sample; the liquid sampling mechanism has a Liquid sampling needle for sucking and adding liquid samples; the nitrogen blowing mechanism is used for nitrogen blowing and concentration of the sample; the liner grabbing mechanism is used for grabbing and moving the liner; the solvent supply mechanism is used for providing extraction solvent The vortex mixing mechanism is used for vortex mixing of the sample; the incubation mechanism is used for incubating the sample; the aging mechanism is used for the aging of the solid-phase microextraction extraction head; the multi-directional movement mechanism can automatically The solid-phase microextraction mechanism, the liquid sampling mechanism, the nitrogen blowing mechanism or the liner grabbing mechanism are acquired and driven to move. 2. The water sample automatic pretreatment device according to claim 1, characterized in that, the water sample automatic pretreatment device further comprises a tool support, the tool support is arranged on the rack, and the liquid sampling mechanism, The nitrogen blowing mechanism and the liner grabbing mechanism are mounted on the tool holder. 3 . The automatic water sample pretreatment device according to claim 1 , wherein the water sample automatic pretreatment device further comprises a liner rack, and the liner rack is used to place the liner. 4 . 4. The water sample automatic pretreatment device according to claim 1, wherein the water sample automatic pretreatment device further comprises a sample holder, and the sample holder is provided with a plurality of placement positions for placing sample bottles, Each of the placement positions is marked with a position serial number. 5 . The automatic water sample pretreatment device according to claim 1 , wherein the incubation mechanism comprises one or more of a heating component, an oscillating component and an ultrasonic component. 6 . 6. A water sample automatic detection system is characterized in that, comprising a chromatograph and the water sample automatic pretreatment device according to any one of claims 1-5, the water sample automatic pretreatment device can be combined with the chromatograph. The water sample automatic pre-processing device processes the sample and places the sample in the liner for concentration by nitrogen blowing, and then the liner grabbing mechanism grabs the liner and puts it into the chromatograph for injection. Intraoral analytical injection. 7. The water sample automatic detection system according to claim 6, wherein the chromatograph includes but is not limited to a gas chromatograph, a gas chromatograph-mass spectrometer, a gas chromatograph-triple quadrupole mass spectrometer and a comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometer. 8. a water sample automatic pretreatment method using the water sample automatic pretreatment device described in any one of claims 1-5, is characterized in that, comprises the steps: When performing the automatic headspace solid phase microextraction mode, the following steps are included: S1: Add a predetermined amount of water sample to be analyzed into the sample bottle; S2: Control the multi-directional motion mechanism to obtain the solid-phase micro-extraction mechanism, control the multi-directional motion mechanism to drive the solid-phase micro-extraction mechanism to move the sample vial to the incubation mechanism, and incubate the sample vial in the incubation mechanism according to the preset incubation conditions to realize the volatilization to be analyzed. volatile organic compounds in water samples; S3: Control the multi-directional motion mechanism to drive the solid-phase microextraction mechanism to move to the aging mechanism, and place the extraction head on the solid-phase microextraction mechanism into the aging mechanism for aging treatment to remove residual volatile organic compounds; S4: After the sample incubation is completed, the multi-directional motion mechanism is controlled to drive the solid-phase micro-extraction mechanism to move to the incubation mechanism, and the extraction head on the solid-phase micro-extraction mechanism is placed in the sample bottle, and the sample bottle is extracted under preset extraction conditions. volatile organics at the top; S5: After the extraction is completed, the multi-directional motion mechanism is controlled to drive the solid-phase micro-extraction mechanism to move to the chromatographic injection port of the chromatograph, and the extraction head is placed in the chromatographic injection port for sample analysis for the chromatograph to detect and analyze; When the automatic liquid-liquid extraction mode is performed, the following steps are included: s1: add a predetermined amount of water sample to be analyzed into the first sample bottle; add a predetermined amount of desiccant into the second sample bottle; take the first liner for use; s2: control the multi-directional movement mechanism to obtain the liquid sampling mechanism, and control the multi-directional movement mechanism to drive the liquid sampling mechanism to move to the solvent supply mechanism to extract a predetermined amount of extraction solvent and inject it into the first sample bottle; s3: control the multi-directional motion mechanism to drive the liquid sampling mechanism to move the first sample bottle and move it into the vortex oscillation mechanism for vortex mixing, and let it stand for a predetermined time to extract the organic matter in the water sample to be analyzed; s4: Control the multi-directional movement mechanism to drive the liquid sampling mechanism to absorb the layered supernatant in the first sample bottle and transfer it to the second sample bottle, and control the multi-directional movement mechanism to drive the liquid sampling mechanism to move the second sample bottle Vortex mixing in the vortex shaking mechanism to dry and remove water; s5: control the multi-directional motion mechanism to drive the liquid sampling mechanism to extract a predetermined amount of liquid from the second sample bottle and add it to the first liner; s6: Control the multi-directional motion mechanism to release the liquid sampling mechanism and obtain the nitrogen blowing mechanism, control the multi-directional motion mechanism to drive the nitrogen blowing mechanism to move into the first liner, and perform nitrogen blowing on the liquid in the first liner to remove the solvent and realize the sample concentrated enrichment; s7: Control the multi-directional motion mechanism to release the nitrogen blowing mechanism and obtain the liner grabbing mechanism, control the multi-directional motion mechanism to drive the liner grabbing mechanism to move to the chromatographic injection port of the chromatograph, and control the multi-directional motion mechanism to drive the liner grabber The taking mechanism moves the first liner into the injection port of the chromatograph for detection and analysis by the chromatograph. 9 . The method for automatic pretreatment of water samples according to claim 8 , wherein a predetermined amount of filler is added to the spare first liner, and the filler comprises glass wool or an adsorbent. 10 . 10. The method for automatic pretreatment of water samples according to claim 8 or 9, characterized in that, when carrying out the automatic headspace solid-phase microextraction mode, when adding a predetermined amount of the water sample to be analyzed into the sample bottle, it is also added at the same time. a predetermined amount of sodium chloride; And/or, when the automatic liquid-liquid extraction mode is performed, a predetermined amount of a demulsifier is also added at the same time when a predetermined amount of the water sample to be analyzed is added to the first sample bottle. 11. The method for automatic pretreatment of water samples according to claim 8 or 9, characterized in that, two modes of automatic headspace solid-phase micro-extraction mode and automatic liquid-liquid extraction mode are controlled to automatically switch, so as to automatically perform different methods on water samples. The pre-processing method is used to realize the detection of different types of targets. The automatic switching process is as follows: The steps of performing the automatic headspace solid-phase microextraction mode are saved as a first method file, and the automatic liquid-liquid extraction mode is saved as a second method file; A running sequence table is set in the automatic water sample pretreatment device, and the position serial number of the sample rack where each sample bottle is located and the first method file or second method file corresponding to the sample bottle are filled in the running sequence table, and the The water sample automatic preprocessing device sequentially loads the first method file or the second method file corresponding to each sample to process the samples in the sample vials at the corresponding positions according to the running sequence table.

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