A pretreatment device for the determination of adsorbable organic halogens

Abstract

This invention provides a pretreatment device for the determination of adsorbable organic halogens, comprising a sample bottle with an upper opening and a lower opening, a shaking adsorption kit, a filtration kit, a column adsorption kit, and a main assembly. The shaking adsorption kit includes an upper sealing cap that can be closed to the upper opening and a lower sealing cap that can be closed to the lower opening. The filtration kit includes a sample cup and a fastening cap. The bottom of the sample cup has a sand core structure that adapts to the lower opening. The fastening cap can fix the sample cup at the lower opening. The column adsorption kit includes an adsorption column and a fastening ring. The upper end of the adsorption column adapts to the lower opening. The fastening ring can fix the adsorption column at the lower opening. The main assembly includes a shell, a shaking assembly, and a vacuum filtration assembly. The pretreatment device for the determination of adsorbable organic halogens described in this invention has a reasonable structural design, high integration, reduces repetitive operations, reduces the number of times samples are transferred between different containers and devices, is easy to operate, saves time and effort, and has high work efficiency.

Description

Technical Field

[0001] This invention belongs to the field of analytical technology of adsorbable organic halogens, and in particular relates to a pretreatment device for the determination of adsorbable organic halogens. Background Technology

[0002] Most organohalogenated compounds (OHCCs) are persistent organic pollutants, characterized by their reluctance to degrade, environmental persistence, and chemical stability. They continuously migrate, transform, accumulate, and bioaccumulate within ecosystems, making them a class of pollutants harmful to the ecological environment. Some OHCCs have been proven to have potential carcinogenic and mutagenic properties, and organisms struggle to effectively eliminate them through metabolic processes, thus easily accumulating along the food chain and harming organismal health. However, due to the complex structure and large number of OHCCs, it is impossible to detect each one individually. Currently, adsorbable organic halogens (AOX) serve as a comprehensive indicator reflecting the pollution level of OHCCs and play a crucial role in the control of OHCC pollution.

[0003] AOX compounds meet two criteria: water solubility (meaning they can dissolve in water) and adsorption by activated carbon (meaning they can be adsorbed onto activated carbon using appropriate methods). Current detection methods employ oscillatory adsorption or column adsorption during pretreatment to adsorb AOX from the sample onto activated carbon, thus extracting key AOX molecules. This is a crucial step in accurately determining AOX.

[0004] Currently, AOX pretreatment requires multiple devices, with samples needing to be transferred between different containers. This process is complex, time-consuming, labor-intensive, inefficient, and prone to sample loss or introducing additional contamination. For example, oscillatory adsorption requires a horizontal shaker and a filtration device. The sample is first oscillated and adsorbed using a horizontal shaker before being transferred to a filtration device. The filtration device mostly filters the sample onto a filter membrane, which is then transferred to an adsorbable organic halogen combustion furnace or the instrument's autosampler. During the transfer process, a small amount of activated carbon may remain, causing sample loss. There is also a possibility of contamination during the transfer process, affecting the accuracy of the measurement results. Column adsorption requires a series adsorption column and a test column, usually using argon or nitrogen to provide filtration pressure. The column structure is complex, requiring high airtightness of the device and an additional gas source, resulting in higher costs. In some cases, simultaneous oscillatory adsorption and column adsorption are required, necessitating even more equipment, making the operation even more cumbersome and time-consuming. Summary of the Invention

[0005] In view of this, in order to solve the above problems, the present invention proposes a pretreatment device for the determination of adsorbable organic halogens with reasonable structural design, high integration, reduced repetitive operations, reduced number of sample transfers between different containers and devices, simple operation, time and labor saving, and high working efficiency.

[0006] To achieve the above objectives, the technical solution of the present invention is implemented as follows:

[0007] A pretreatment device for the determination of adsorbable organic halogens, characterized in that it comprises:

[0008] A sample bottle, wherein the sample bottle has an upper opening and a lower opening, the upper opening and the lower opening are connected (liquid can flow through), and the number of the sample bottles is at least one;

[0009] The oscillating adsorption kit includes an upper sealing cap that can tightly close to the upper opening and a lower sealing cap that can tightly close to the lower opening; that is, when in use, the upper sealing cap and the lower sealing cap can be installed on the sample bottle, and when not in use, they can be removed.

[0010] A filter kit includes a sample cup and a fastening cap. The sample cup has a sand core structure at the bottom and is open at the top, adapting to the lower opening. The fastening cap is open at both ends and connected. The fastening cap can be fitted onto the outside of the sample cup and the lower opening, detachably fixing the sample cup to the lower opening. In use, the sample cup can be installed at the lower opening of the sample bottle and fixed in place by the fastening cap.

[0011] A column adsorption kit includes an adsorption column and a fastening ring; the upper end of the adsorption column is adapted to the lower opening; the fastening ring can detachably fix the adsorption column to the lower opening; that is, in use, the adsorption column can be installed at the lower opening of the sample vial and fixed in place by the fastening ring.

[0012] The main component includes a housing, an oscillation assembly mounted on the housing, and a filtration assembly. The oscillation assembly includes an oscillating shaker, an oscillation power device for driving the oscillating shaker, and an oscillation sample clamp disposed on the oscillating shaker for fixing the sample bottle. The filtration assembly includes a filtration pipe, a filtration power device connected to the filtration pipe, and a filtration sample clamp for fixing the sample bottle. The filtration pipe is provided with a connector for connecting to the lower end of the fastening cap and the lower end of the adsorption column.

[0013] Application process: It can perform oscillation adsorption treatment alone, column adsorption treatment alone, or both oscillation adsorption and column adsorption treatment simultaneously.

[0014] The process of the oscillation adsorption treatment is as follows:

[0015] 1) Oscillating adsorption process:

[0016] Tightly seal the lower cap onto the lower opening of the sample vial. Inject a certain volume of pretreated sample into the sample vial, add activated carbon, and then tightly seal the upper cap onto the upper opening of the sample vial, ensuring that the assembled sample vial kit is leak-proof. Place the sample vial kit horizontally on the shaking sample clamp, which holds the sample vial kit. Start the shaking power device to drive the shaking shaker to shake and adsorb the sample. After shaking for a period of time, turn off the shaking power device and remove the sample vial kit after shaking. The shaking adsorption is complete.

[0017] 2) Filtration process:

[0018] After the sample vial assembly has completed oscillation and adsorption, invert it, remove the lower sealing cap, install the sample cup upside down at the lower opening, and fit the upper end of the fastening cap over the outside of the sample cup and the lower opening, and fix it to the lower opening to obtain the sample vial assembly; connect the lower end of the fastening cap to the connector through the rubber tube, and then connect it to the vacuum filtration pipe, straighten the sample vial, hold the sample vial with the vacuum filtration sample clamp, remove the upper sealing cap, start the vacuum filtration power device, and perform vacuum filtration on the sample. After vacuum filtration, wash it clean with sodium nitrate-nitric acid solution, turn off the vacuum filtration power device, and remove the sample vial assembly;

[0019] Remove the fastening cap and the sample cup. The sample cup now contains activated carbon particles that have adsorbed AOX. Transfer the sample cup directly to an autosampler that can adsorb organic halogens for analysis.

[0020] The process of column adsorption is as follows:

[0021] Place the adsorption column into the fastening ring, allowing the lower half of the column to pass through. Align the top of the adsorption column with the lower opening of the sample vial, securing the opening with the fastening ring. This fixes the adsorption column onto the lower opening, creating the sample vial assembly. Connect the lower end of the adsorption column to the connector via a rubber tube, which in turn connects to the filtration pipeline. Straighten the sample vial and hold it with the filtration sample clamp. Pour the pretreated sample into the vial through the upper opening. Start the filtration power unit to filter the sample. After filtration, wash the sample thoroughly with sodium nitrate-nitric acid solution, then turn off the filtration power unit and remove the sample vial assembly.

[0022] Remove the fastening ring and take out the adsorption column for further processing.

[0023] Preferably, the sample bottle has vertical graduations along its body.

[0024] Preferably, the main body of the sample bottle is cylindrical with a tapered lower end, resembling an inverted bottle structure.

[0025] Preferably, the sample vial is made of borosilicate glass.

[0026] Preferably, the upper opening and the upper sealing cover, and the lower opening and the lower sealing cover are detachably connected by threaded engagement.

[0027] Preferably, an upper gasket is installed inside the upper sealing cover, and a lower sealing gasket is installed inside the lower sealing cover.

[0028] Preferably, the upper sealing cover and the lower sealing cover are made of plastic, and the upper gasket and the lower sealing gasket are made of polytetrafluoroethylene.

[0029] Preferably, the sample cup has a cylindrical cup-shaped structure with an outer edge at its bottom. The outer diameter of the upper end of the sample cup is the same as the inner diameter of the lower opening. The upper end of the sample cup can be inserted into the lower opening, and the outer edge can abut against the bottom of the lower opening to prevent the sample cup from falling into the sample bottle. The fastening cap is T-shaped, with an internal thread in its upper cavity, and can be fitted onto the outer edge. The lower opening has an external thread, and the upper part of the fastening cap can be screwed into the lower opening.

[0030] In use, the upper end of the sample cup is inserted into the lower opening of the sample vial, and the outer edge of the sample cup rests against the bottom of the lower opening. The upper inner cavity of the fastening cap can fit over the outer edge and be fixed by threaded connection with the external thread of the lower opening.

[0031] Preferably, the sample cup is made of quartz, which is resistant to high temperatures.

[0032] Preferably, the adsorption column includes a syringe-shaped column shell and an adsorption core disposed inside the column shell; the top outer edge of the column shell protrudes outward and its outer diameter is consistent with the outer diameter of the lower opening, and can abut against the bottom of the lower opening; the inner wall of the fastening ring is provided with internal threads, the lower opening is provided with external threads, and the fastening ring can be sleeved on the outside of the column shell and the lower opening, and the adsorption column is fixed at the lower opening by means of thread engagement.

[0033] When using, insert the adsorption column into the fastening ring. The lower half of the adsorption column passes through the fastening ring, while the top outer edge is located inside the fastening ring and locked onto the bottom surface of the fastening ring. Align the assembled adsorption column and fastening ring with the bottom opening of the sample vial. Tighten the fastening ring onto the bottom opening by screwing it in. After tightening, the top of the adsorption column will fit tightly against the bottom opening.

[0034] Preferably, the cylindrical shell is made of borosilicate glass.

[0035] Preferably, the adsorption core includes, from bottom to top, a first gasket layer, a first activated carbon layer, a second gasket layer, a third activated carbon layer, and a second gasket layer.

[0036] After the column adsorption process is completed, the first activated carbon layer in the adsorption column is used to determine the AOX in the sample, and the second activated carbon layer is used to check whether the adsorption is qualified.

[0037] Preferably, the first gasket layer, the second gasket layer, and the third gasket layer are all high-temperature dehalogenated quartz wool.

[0038] Preferably, the activated carbon in the first activated carbon layer and the second activated carbon layer has an iodine value ≥1050, a chloride content <0.0015%, and a particle size of 50μm to 100μm.

[0039] Preferably, the oscillation power device includes a DC motor installed inside the housing, a rotating shaft connected to the output end of the DC motor, a central rotating platform driven by the rotating shaft, and a transmission shaft installed on the central rotating platform; the top of the transmission shaft is connected to the oscillating shaker; the oscillating shaker is installed on the top of the housing, and a plurality of rollers are provided between the bottom of the oscillating shaker and the top of the housing, the rollers being able to roll within a fixed track.

[0040] The housing is equipped with an oscillation switch and an oscillation speed adjustment knob. The oscillation switch controls the start and stop of the DC motor, and the oscillation speed adjustment knob controls the speed of the DC motor.

[0041] After the DC unit is started, the rotating shaft begins to rotate, driving the central rotating platform and the transmission shaft to begin regular circular motion. This motion is transmitted to the vibrating shaker, which begins periodic horizontal oscillation. The rollers provide support for the vibrating shaker. When the vibrating shaker moves, the rollers roll within a fixed track, reducing friction.

[0042] Preferably, the oscillating sample clamp includes a support rod mounted on the oscillating shaker, a clamp mounted on the top of the support rod, and a locking bolt for controlling the clamping tightness of the clamp; the clamp can hold the sample bottle, and the locking bolt can control the tightness of the clamping.

[0043] Preferably, there are multiple oscillating sample clamps, arranged in groups of two on the oscillating shaker; each group of two oscillating sample clamps can hold one sample bottle.

[0044] Preferably, the filtration pipe is provided with multiple connectors; each connector includes a connecting pipe with one end connected to the filtration pipe and a rotary switch installed on the connecting pipe; the other end of the connecting pipe can be connected to the lower end of the fastening cover and the lower end of the adsorption column.

[0045] Preferably, the filtration pipe is made of stainless steel, and the inner wall of the filtration pipe is coated with polytetrafluoroethylene to prevent acidic samples from corroding the pipe.

[0046] Preferably, there are two sets of filtration pipes, symmetrically arranged on the two outer side walls of the housing.

[0047] Preferably, the filtration power unit includes a filtration pump installed in the housing, a filtration main pipe with one end connected to the filtration port of the filtration pump, and a liquid buffer bottle connected to the other end of the filtration main pipe; the other end of the liquid buffer bottle is connected to the outlet end of the filtration pipe.

[0048] The housing is equipped with a filtration switch and a suction force adjustment knob. The filtration switch controls the start and stop of the filtration pump, and the suction force adjustment knob controls the suction force of the filtration pump.

[0049] Preferably, the filtration sample clamp includes a support rod mounted on the housing, a clamp mounted on the top of the support rod, and a locking bolt for controlling the clamping degree of the clamp.

[0050] Preferably, there are multiple sample holders for vacuum filtration, each corresponding to one of the connectors.

[0051] Compared with existing technologies, the pretreatment device for the determination of adsorbable organic halogens described in this invention has the following advantages:

[0052] (1) The pretreatment device for the determination of adsorbable organic halogens described in this invention integrates the oscillation adsorption, column adsorption and filtration system into one. It has a reasonable structural design, high integration, small footprint, reduces the number of times samples are transferred between different containers and various devices, simplifies operation, saves time and effort, and effectively improves work efficiency. It can realize the oscillation adsorption treatment method alone, or the column adsorption treatment method alone, or the oscillation adsorption and column adsorption treatment methods simultaneously.

[0053] (2) The pretreatment device for the determination of adsorbable organic halogens described in this invention adopts a modular design scheme. By replacing different accessories, multiple adsorption / filtration methods can be achieved, which saves instrument costs, reduces the number of sample transfers, and facilitates disassembly and cleaning.

[0054] (3) The pretreatment device for the determination of adsorbable organic halogens described in this invention uses a filter kit instead of a traditional funnel and a sample cup with a sand core structure at the bottom instead of a filter membrane for filtration. The sample cup does not need to transfer the sample and can be directly sent into the subsequent processing instrument, which solves the problems of activated carbon retention and possible contamination during the transfer process.

[0055] (4) The column adsorption kit of the pretreatment device for the determination of adsorbable organic halogens described in this invention uses a vacuum pump as a pressure source, which does not require an additional gas source and saves costs.

[0056] (5) The pretreatment device for the determination of adsorbable organic halogens described in this invention can simultaneously perform oscillation adsorption and column adsorption on unknown samples to obtain more accurate results, save time on repeated experiments, and save time and effort. Attached Figure Description

[0057] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an undue limitation of the invention. In the drawings:

[0058] Figure 1 This is a schematic diagram of the sample bottle structure according to an embodiment of the present invention;

[0059] Figure 2 This is a schematic diagram of the structure of the oscillating adsorption kit described in an embodiment of the present invention;

[0060] Figure 3 This is a schematic diagram illustrating the installation of the oscillating adsorption kit and sample bottle according to an embodiment of the present invention;

[0061] Figure 4 This is a schematic diagram of the structure of the filter kit described in an embodiment of the present invention;

[0062] Figure 5 This is a schematic diagram illustrating the installation of the filter kit and sample bottle according to an embodiment of the present invention;

[0063] Figure 6 This is a schematic diagram of the column adsorption kit described in an embodiment of the present invention;

[0064] Figure 7 This is a schematic diagram illustrating the installation of the column adsorption kit and sample bottle according to an embodiment of the present invention;

[0065] Figure 8 This is a schematic diagram of the main component described in an embodiment of the present invention;

[0066] Figure 9 This is a schematic diagram of the internal structure of the main component described in an embodiment of the present invention;

[0067] Figure 10 This is a schematic diagram showing the assembly completed during the oscillating adsorption process described in an embodiment of the present invention;

[0068] Figure 11 This is a schematic diagram showing the completed assembly process during the filtration process following oscillation adsorption as described in an embodiment of the present invention;

[0069] Figure 12This is a schematic diagram showing the completed assembly during the column adsorption process described in an embodiment of the present invention.

[0070] Explanation of reference numerals in the attached figures:

[0071] 1-Sample vial, 11-Top opening, 12-Bottom opening;

[0072] 2-Oscillating adsorption kit, 21-Upper sealing cap, 22-Upper sealing gasket, 23-Lower sealing cap, 24-Lower sealing gasket;

[0073] 3-Filter kit, 31-Sample cup, 311-Sand core structure, 312-Outer edge, 32-Fastening cap;

[0074] 4-Column adsorption kit, 41-Adsorption column, 411-Column shell, 412-Gasket layer one, 413-Activated carbon layer one, 414-Gasket layer two, 415-Activated carbon layer two, 416-Gasket layer three, 42-Fastening ring;

[0075] 5-Main Components

[0076] 51-Housing housing, 511-Oscillation switch, 512-Oscillation speed adjustment knob, 513-Filtering switch, 514-Suction force adjustment knob

[0077] 52-Oscillating assembly, 521-Oscillating shaker, 522-Oscillating sample holder, 523-DC motor, 524-Rotating shaft, 525-Central rotating platform, 526-Drive shaft, 527-Roller.

[0078] 53-Filter assembly, 531-Filter tubing, 532-Filter sample holder, 533-Connector, 5331-Connecting tube, 5332-Tube switch, 534-Filter pump, 535-Filter main tube, 536-Liquid buffer bottle;

[0079] 6-Rubber hose. Detailed Implementation

[0080] It should be noted that, unless otherwise specified, the embodiments and features described in the present invention can be combined with each other.

[0081] In the description of this invention, it should be understood that the terms "center," "longitudinal," "lateral," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," and "outer," etc., indicating orientations or positional relationships, are based on the orientations or positional relationships shown in the accompanying drawings and are used only for the convenience of describing the invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation of the invention. In the description of this invention, unless otherwise stated, "a plurality of" means two or more.

[0082] In the description of this invention, it should be noted that, unless otherwise explicitly specified and limited, the terms "installation," "connection," and "linking" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal connection of two components. Those skilled in the art will understand the specific meaning of the above terms in this invention based on the specific circumstances.

[0083] The present invention will now be described in detail with reference to the accompanying drawings and embodiments.

[0084] like Figures 1 to 9 As shown, a pretreatment device for the determination of adsorbable organic halogens includes a sample bottle 1, a shaking adsorption kit 2, a filter kit 3, a column adsorption kit 4, and a main body assembly 5.

[0085] The sample bottle 1 is made of high borosilicate glass. The main body of the sample bottle 1 is a cylindrical structure with a tapered bottom. It has vertical graduations along the bottle body. The sample bottle 1 has an upper opening 11 at the top and a lower opening 12 at the bottom. The upper opening 11 and the lower opening 12 are connected. The upper opening 11 and the lower opening 12 have external threads on their outer sides. There is at least one sample bottle 1.

[0086] The oscillating adsorption kit 2 includes an upper sealing cap 21, an upper sealing gasket 22, a lower sealing cap 23, and a lower sealing gasket 24. The upper sealing cap 21 is made of plastic and has an internal thread on its inner side that matches the external thread of the upper opening 11. The upper sealing gasket 22 is made of polytetrafluoroethylene and can be placed inside the upper sealing cap 21. When in use, it can be tightly connected to the upper sealing cap 21 and the upper opening of the sample bottle 1 to achieve a sealing effect. The lower sealing cap 23 is made of plastic and has an internal thread on its inner side that matches the external thread of the lower opening 12. The lower sealing gasket 24 is made of polytetrafluoroethylene and can be placed inside the lower sealing cap 23. When in use, it can be tightly connected to the lower sealing cap 23 and the lower opening 12 of the sample bottle 1 to achieve a sealing effect.

[0087] The filter kit 3 includes a sample cup 31 and a fastening cap 32. The sample cup 31 is made of quartz and has a cylindrical cup-shaped structure with an open top and a sand core structure 311 at the bottom. An outer edge 312 is provided on the outer side of the bottom end. The outer diameter of the upper end of the sample cup 31 is the same as the inner diameter of the lower opening 12. The upper end of the sample cup 31 can be inserted into the lower opening 12 and fit tightly. The diameter of the outer edge 312 is the same as the outer diameter of the lower opening 12 and can abut against the bottom of the lower opening 12. The fastening cap 32 is "T" shaped, with an open and connected upper and lower end. Its upper inner cavity is provided with an internal thread that is compatible with the external thread of the lower opening 12. The upper part of the fastening cap 32 can be fitted onto the outer side of the outer edge 312. The upper part of the fastening cap 32 can be fixed to the lower opening 12 by screwing on the thread.

[0088] The column adsorption kit 4 includes an adsorption column 41 and a fastening ring 42; the adsorption column 41 includes a column shell 411 and an adsorption core disposed within the column shell 41; the column shell 41 is made of high borosilicate glass, and the column shell 41 is syringe-shaped, with the outer edge of the top of the column shell 41 protruding outward, and its outer diameter being consistent with the outer diameter of the lower opening 12, so that it can be tightly fitted to the bottom of the lower opening 12; the adsorption core includes, from bottom to top, a first gasket layer 412, a first activated carbon layer 413, a second gasket layer 414, a second activated carbon layer 415, and a third gasket layer 416; the first gasket layer 414... 12. Gasket layer 2 414 and gasket layer 3 416 are both high-temperature dehalogenated quartz wool; the activated carbon in activated carbon layer 1 413 and activated carbon layer 2 415 has an iodine value ≥1050, a chloride content <0.0015%, and a particle size of 50μm~100μm; the inner wall of the fastening ring 42 is provided with an internal thread that is compatible with the external thread of the lower opening 12. The fastening ring 42 can be sleeved on the outer edge of the top protruding part of the column shell 411 and the outer side of the lower opening 12, and the adsorption column 41 is fixed at the lower opening 12 by the thread engagement.

[0089] The main component 5 includes a rectangular shell 51, an oscillation assembly 52 mounted on the shell 51, and a filtration assembly 53;

[0090] The oscillation assembly 52 includes an oscillating shaker 521, an oscillation power device for driving the oscillating shaker 521, and an oscillation sample clamp 522 mounted on the oscillating shaker 521 to fix the sample vial 1. The oscillation power device includes a DC motor 523 installed in the housing 51, a rotating shaft 524 connected to the output end of the DC motor 523, a central rotating platform 525 driven by the rotating shaft 524, and a transmission shaft 526 mounted on the central rotating platform 525. The top of the transmission shaft 526 is connected to the oscillating shaker 521. The oscillating shaker 521 is mounted on... Multiple rollers 527 are provided between the top of the housing 51, the bottom of the shaking table 521, and the top of the housing 51. The rollers 527 can roll within a fixed track. The shaking sample clamp 522 includes a support rod mounted on the shaking table 521, a clamp mounted on the top of the support rod, and a locking bolt for controlling the clamping tightness. The clamp can hold the sample bottle 1, and the locking bolt can control the tightness of the clamp. There are multiple shaking sample clamps 522, arranged in groups of two on the shaking table 521. Each group of two shaking sample clamps 522 can hold one sample bottle 1.

[0091] The filtration assembly 53 includes a filtration pipe 531, a filtration power unit connected to the filtration pipe 531, and a filtration sample clamp 532 for fixing the sample vial 1. The filtration pipe 531 is made of stainless steel, and its inner wall is coated with polytetrafluoroethylene to prevent acidic samples from corroding the pipe. There are two sets of filtration pipes 531, symmetrically arranged on the two outer walls of the housing 51. Multiple connectors 533 are provided on the filtration pipe 531. Each connector 533 includes a connecting pipe 5331 with one end connected to the filtration pipe 531, and a rotary switch 5332 mounted on the connecting pipe 5331. The other end can be connected to the lower end of the fastening cap 32 and the lower end of the adsorption column 41; the filtration power device includes a filtration pump 534 installed in the housing 51, a filtration main pipe 535 connected at one end to the filtration port of the filtration pump 534, and a liquid buffer bottle 536 (which can be removed from the housing) connected to the other end of the filtration main pipe 535, the other end of the liquid buffer bottle 536 being connected to the outlet end of the filtration pipe 531; the filtration sample clamp 532 includes a support rod installed on the housing 51, a clamp installed on the top of the support rod, and a locking bolt for controlling the clamping degree; there are multiple filtration sample clamps 532, which are set one-to-one with the connector 533;

[0092] The housing 51 is equipped with an oscillation switch 511 and an oscillation speed adjustment knob 512. The oscillation switch 511 controls the start and stop of the DC motor 523, and the oscillation speed adjustment knob 512 controls the speed of the DC motor 523. After the DC motor 523 starts, the rotating shaft 524 starts to rotate, driving the central rotating platform 525 and the transmission shaft 526 to start regular circular motion, which is transmitted to the vibrating shaker 521 to start periodic horizontal oscillation. The housing 51 is equipped with a filtration switch 513 and a suction force adjustment knob 514. The filtration switch 513 controls the start and stop of the filtration pump 534, and the suction force adjustment knob 514 controls the suction force of the filtration pump 513.

[0093] The pretreatment device for the determination of adsorbable organic halogens described in this embodiment can perform oscillation adsorption alone, column adsorption alone, or both oscillation adsorption and column adsorption simultaneously. The specific working process is as follows:

[0094] 1-1) Oscillating adsorption process (e.g.) Figure 10 As shown, this is the assembled structure:

[0095] Place the lower sealing gasket 24 inside the lower sealing cap 23, tighten the lower sealing cap 23 to the lower opening 12 of the sample bottle 1, inject a certain volume of pretreated sample into the sample bottle 1, add activated carbon, place the upper sealing gasket 22 inside the upper sealing cap 21, tighten the upper sealing cap 21 to the upper opening 11 of the sample bottle 1 to ensure that the assembled sample bottle kit does not leak; place the sample bottle kit horizontally on the vibrating sample clamp 522, tighten the locking bolt on the vibrating sample clamp 522, and the vibrating sample clamp 522 holds the sample bottle kit; turn on the vibration switch 511, adjust the vibration frequency by adjusting the vibration speed knob 512, and vibrate and adsorb the sample. After vibrating for a period of time, turn off the vibration switch 511, loosen the locking bolt on the vibrating sample clamp 522, remove the sample bottle kit, and the vibration and adsorption is complete;

[0096] 1-2) Filtration process after oscillation adsorption (e.g.) Figure 11 As shown, this is the assembled structure:

[0097] After the sample vial assembly has completed its oscillation and adsorption process, invert it and unscrew the lower sealing cap 24. Insert the sample cup 31 upside down into the lower opening 12, with the outer edge 312 of the sample cup 31 resting against the lower opening 12. Place the upper end of the fastening cap 32 over the sample cup 31 and the lower opening 12 and tighten it with the threads to obtain the sample vial assembly. Connect the connecting tube 5331 to the fastening cap 32 using the rubber tube 6. Then, straighten the sample vial 1 and fix it with the vacuum filtration sample clamp 532. Tighten the vacuum filtration sample clamp. Remove the locking bolt on the sample clamp 532; remove the upper sealing cap 21, open the knob switch 5332 on the connecting tube 5331, open the vacuum filter switch 513, adjust the vacuum force by adjusting the vacuum force knob 514, control the vacuum force of a single sample bottle 1 by adjusting the knob switch 5332, filter the sample, wash it clean with sodium nitrate-nitric acid solution after filtration, close the knob switch 5332, close the vacuum filter switch 513, loosen the locking bolt on the vacuum filter sample clamp 532, and remove the sample bottle kit;

[0098] Remove the fastening cap 32 and the sample cup 31. The sample cup 31 contains activated carbon particles that have adsorbed AOX. Transfer the sample cup 31 directly to an autosampler that can adsorb organic halogens for analysis.

[0099] 2. Column adsorption process (e.g.) Figure 12 As shown, this is the assembled structure:

[0100] The first gasket layer 412, the first activated carbon layer 413, the second gasket layer 414, the second activated carbon layer 415, and the third gasket layer 416 are sequentially filled into the column shell 411 to form the adsorption column 41. The adsorption column 41 is placed into the fastening ring 42, with the lower half of the adsorption column 41 passing through the fastening ring 42 and the outer edge of the top located inside the fastening ring 42 and locked onto the bottom surface of the fastening ring 42. The assembled adsorption column 41 and fastening ring 42 are then aligned with the lower opening 12 of the sample bottle 1. The fastening ring 42 is screwed onto the lower opening 12 by screwing on the thread. After tightening, the top of the adsorption column 41 is tightly fitted onto the lower opening 12. The connecting tube 5331 is connected to the lower end of the adsorption column 41 using the rubber tube 6. The sample bottle 1 is then straightened, and the sample clamp 532 is used for vacuum filtration. Fix sample bottle 1 and tighten the locking bolt on the filtration sample clamp 532; inject the pretreated sample into sample bottle 1 through the upper opening 11; turn on the knob switch 5332 on the connecting tube 5331 and turn on the filtration switch 513; adjust the filtration force by adjusting the filtration force knob 514; control the filtration force of a single sample bottle 1 by adjusting the filtration force knob 5332; after filtration, wash with sodium nitrate-nitric acid solution; turn off the knob switch 5332 and the filtration switch 513; loosen the locking bolt on the filtration sample clamp 532; loosen the connection between the rubber tube 6 and the adsorption column 41; and unscrew the fastening ring 42. At this time, the activated carbon layer 413 in the adsorption column 41 is used to determine AOX in the sample, and the activated carbon layer 415 is used to check whether the adsorption is qualified.

[0101] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A pretreatment device for the determination of adsorbable organic halogens, characterized in that, include: A sample bottle, wherein the sample bottle has an upper opening and a lower opening, the upper opening and the lower opening are connected, and the number of the sample bottles is at least one; An oscillating adsorption kit, the oscillating adsorption kit including an upper sealing cap that can be closed to the upper opening and a lower sealing cap that can be closed to the lower opening; A filter kit, comprising a sample cup and a fastening cap; the sample cup has a sand core structure at the bottom and is open at the top, adapting to the lower opening; The fastening cap is open and connected at the top and bottom. The fastening cap can be sleeved on the outside of the sample cup and the lower opening to detachably fix the sample cup to the lower opening. A column adsorption kit, comprising an adsorption column and a fastening ring; the upper end of the adsorption column is adapted to the lower opening; the fastening ring can detachably fix the adsorption column to the lower opening; The main component includes a housing, an oscillation assembly mounted on the housing, and a filtration assembly. The oscillation assembly includes an oscillating shaker, an oscillation power device for driving the oscillating shaker, and an oscillation sample clamp disposed on the oscillating shaker for fixing the sample bottle. The filtration assembly includes a filtration pipe, a filtration power device connected to the filtration pipe, and a filtration sample clamp for fixing the sample bottle. The filtration pipe is provided with a connector for connecting to the lower end of the fastening cap and the lower end of the adsorption column.

2. The pretreatment apparatus for determining adsorbable organic halogens according to claim 1, characterized in that: The sample bottle has vertical graduations along its body.

3. The pretreatment apparatus for the determination of adsorbable organic halogens according to claim 1, characterized in that: The sample vial has a cylindrical structure with a tapered bottom.

4. The pretreatment apparatus for determining adsorbable organic halogens according to claim 1, characterized in that: The sample vials are made of borosilicate glass.

5. The pretreatment apparatus for determining adsorbable organic halogens according to claim 1, characterized in that: The upper opening and the upper sealing cover, as well as the lower opening and the lower sealing cover, are detachably connected by threaded engagement.

6. The pretreatment apparatus for the determination of adsorbable organic halogens according to claim 5, characterized in that: An upper gasket is installed inside the upper sealing cover, and a lower sealing gasket is installed inside the lower sealing cover.

7. The pretreatment apparatus for the determination of adsorbable organic halogens according to claim 6, characterized in that: The upper sealing cap and the lower sealing cap are made of plastic, and the upper gasket and the lower sealing gasket are made of polytetrafluoroethylene.

8. The pretreatment apparatus for the determination of adsorbable organic halogens according to claim 1, characterized in that: The sample cup has a cylindrical cup-shaped structure with an outer edge at its bottom. The outer diameter of the upper end of the sample cup is the same as the inner diameter of the lower opening. The upper end of the sample cup can be inserted into the lower opening, and the outer edge can abut against the bottom of the lower opening. The fastening cap is "T"-shaped, with an internal thread in its upper cavity, and can be fitted onto the outer edge. The lower opening has an external thread, and the upper part of the fastening cap can be screwed into the lower opening.

9. The pretreatment apparatus for the determination of adsorbable organic halogens according to claim 1, characterized in that: The sample cup is made of quartz.

10. The pretreatment apparatus for the determination of adsorbable organic halogens according to claim 1, characterized in that: The adsorption column includes a syringe-shaped column shell and an adsorption core disposed inside the column shell; the top outer edge of the column shell protrudes outward and its outer diameter is consistent with the outer diameter of the lower opening, and it can abut against the bottom of the lower opening; the inner wall of the fastening ring is provided with internal threads, the lower opening is provided with external threads, and the fastening ring can be sleeved on the outside of the column shell and the lower opening, and the adsorption column is fixed at the lower opening by means of thread engagement.

11. The pretreatment apparatus for the determination of adsorbable organic halogens according to claim 10, characterized in that: The shell is made of borosilicate glass.

12. The pretreatment apparatus for the determination of adsorbable organic halogens according to claim 10, characterized in that: The adsorption core comprises, from bottom to top, a first gasket layer, a first activated carbon layer, a second gasket layer, a third activated carbon layer, and a third gasket layer.

13. The pretreatment apparatus for the determination of adsorbable organic halogens according to claim 12, characterized in that: The first gasket layer, the second gasket layer, and the third gasket layer are all high-temperature dehalogenated quartz wool; the activated carbon in the first activated carbon layer and the second activated carbon layer has an iodine value ≥1050, a chloride content <0.0015%, and a particle size of 50μm to 100μm.

14. The pretreatment apparatus for the determination of adsorbable organic halogens according to any one of claims 1 to 13, characterized in that: The oscillation power device includes a DC motor installed inside the housing, a rotating shaft connected to the output end of the DC motor, a central rotating platform driven by the rotating shaft, and a transmission shaft installed on the central rotating platform; the top of the transmission shaft is connected to the oscillating shaker; the oscillating shaker is installed on the top of the housing, and multiple rollers are provided between the bottom of the oscillating shaker and the top of the housing, and the rollers can roll in a fixed track.

15. The pretreatment apparatus for the determination of adsorbable organic halogens according to any one of claims 1 to 13, characterized in that: The oscillating sample clamp includes a support rod mounted on the oscillating shaker, a clamp mounted on the top of the support rod, and a locking bolt for controlling the clamping degree of the clamp.

16. The pretreatment apparatus for the determination of adsorbable organic halogens according to claim 15, characterized in that: The oscillating sample holders are multiple, and are arranged in pairs on the oscillating shaker.

17. The pretreatment apparatus for the determination of adsorbable organic halogens according to any one of claims 1 to 13, characterized in that: The filtration pipe is provided with multiple connectors; each connector includes a connecting pipe with one end connected to the filtration pipe and a rotary switch installed on the connecting pipe; the other end of the connecting pipe can be connected to the lower end of the fastening cover and the lower end of the adsorption column.

18. The pretreatment apparatus for the determination of adsorbable organic halogens according to claim 17, characterized in that: The filtration pipe is made of stainless steel, and the inner wall of the filtration pipe is coated with polytetrafluoroethylene. There are two sets of filtration pipes, symmetrically arranged on the two outer walls of the housing. The filtration power unit includes a filtration pump installed in the housing, a filtration main pipe connected at one end to the filtration port of the filtration pump, and a liquid buffer bottle connected at the other end of the filtration main pipe. The other end of the liquid buffer bottle is connected to the outlet end of the filtration pipe.

19. The pretreatment apparatus for the determination of adsorbable organic halogens according to claim 18, characterized in that: The filtration sample clamp includes a support rod mounted on the housing, a clamp mounted on the top of the support rod, and a locking bolt for controlling the clamping degree of the clamp.

20. The pretreatment apparatus for the determination of adsorbable organic halogens according to claim 19, characterized in that: There are multiple sample holders for vacuum filtration, each corresponding to one of the connectors.

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