Device for removing perfluorinated and polyfluorinated organic matters in experimental water

Abstract

The invention discloses a device for removing perfluorinated and polyfluorinated organic matters in experimental water, which comprises a water feeder, a purification device, a water storage device and an external protective shell, and is characterized in that the water feeder pumps water produced by a laboratory water purifier into the purification device at a constant speed; the purification device is filled with a solid-phase extraction matrix composed of divinyl benzene and glycidyl methacrylate copolymerized porous polymer microspheres and a perfluoroalkyl derivatization layer, and perfluorinated and polyfluorinated organic matters (PFCs) in experimental water can be efficiently and selectively adsorbed; the water storage device is used for storing purified water, and a dual-wavelength ultraviolet lamp is arranged in the top of the water storage device to realize a sterilization function; and the external protective shell realizes fixation and integration of all parts, and has convenience in movement. The method can effectively remove PFCs in experimental water, does not introduce extra impurity pollution, can be matched with various laboratory water purifiers for use, is simple and convenient to operate and low in cost, provides technical guarantee for laboratory quality control of PFCs detection, and solves the technical problem that an existing pure water preparation method cannot effectively remove PFCs.

Description

Technical Field

[0001] This invention relates to the field of instrumental analysis and testing technology, and in particular to a device for removing perfluorinated and polyfluorinated organic compounds from laboratory water. Background Technology

[0002] Perfluorinated compounds (PFCs), due to their stable carbon-fluorine bonds, possess unique hydrophobicity, oil repellency, and high surface activity. Currently, over 4700 PFCs have been synthesized and are widely used in the production of various industrial and consumer products. PFCs pose an emission risk throughout their entire lifecycle, from production and processing to consumption and disposal. These substances can enter surface water through industrial wastewater, domestic sewage, atmospheric deposition, and rainfall. Traditional wastewater treatment methods cannot completely remove them, leading to soil and groundwater contamination through infiltration, and even long-distance transport to seawater, presenting a global pollution trend. PFCs have also been detected in tap water and ambient water bodies in several regions of my country. PFCs exhibit bioaccumulation and can amplify along the food chain. Dietary intake is the main route of human exposure to PFCs, which can cause multi-organ and multi-system toxicity, are associated with some chronic diseases and cancers, and pose a significant potential threat to human health. The International Agency for Research on Cancer (IARC) classifies perfluorooctanoic acid (PFOA) as a Group 1 carcinogen and perfluorooctane sulfonate (PFOS) as a Group 2B carcinogen. In 2022, my country also included some PFCs in the "List of Key Controlled New Pollutants (2023 Edition)".

[0003] The widespread presence of petrochemical fuel cells (PFCs) and their adverse effects on human health have drawn significant attention from the scientific community and the public. Extensive research on PFCs has been conducted by scholars both domestically and internationally, covering external exposure sources such as soil, water, air, and food, as well as biomonitoring areas such as human blood, breast milk, and urine, resulting in a series of exposure assessment findings. Given the diverse types of PFCs and the wide variety of matrices involved, accurate and reliable baseline data for exposure risk assessment are crucial. However, laboratory detection and analysis of PFCs faces the challenge of widespread background contamination, making laboratory quality control a significant challenge in PFC detection and analysis.

[0004] Most PFCs are non-volatile, thermally stable substances that require derivatization before they can be determined by gas chromatography or gas chromatography-tandem mass spectrometry (GC-MS / MS), making the process relatively cumbersome. Furthermore, PFCs do not absorb ultraviolet light or produce fluorescence, making them unsuitable for analysis using high-performance liquid chromatography-ultraviolet or fluorescence detectors. Considering the low concentration and diverse types of PFCs in environmental water bodies, with pollution levels often at the ng / L level, high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS / MS), combined with highly effective pretreatment methods, can overcome the influence of matrix effects and fully leverage its advantages of high sensitivity and selectivity, making it the most commonly used technique for PFC analysis in laboratories. HPLC, as the front-end structure of HPLC-MS / MS, relies on the differences in affinity between the sample components and the stationary and mobile phases to achieve component separation. In practical detection work, researchers typically select a commercially available stationary phase based on the analytical purpose, while the mobile phase consists of organic reagents and pure water in a specific ratio, which needs to be determined experimentally.

[0005] The purified water used in experiments is generally obtained through a purification method combining ion exchange resin and reverse osmosis membrane methods. However, existing experimental data shows that a certain amount of PFCs (polyfluorocarbons) background interference is commonly present in purified water. This interference mainly originates from two aspects: first, thermoplastic fluoroplastics are widely used in components such as pipes, pumps, valves, and seals of water purifiers; second, water purifiers have limited PFC removal capabilities, and for water bodies in areas with high PFC detection, the purification results cannot meet laboratory quality control requirements. When PFC background interference exists in the mobile phase, it directly affects the accuracy and reliability of laboratory test results, causing bias in subsequent in-depth data analysis. Therefore, removing PFCs from the mobile phase is a crucial and essential step in laboratory quality control. (See also...) Figure 1 , Figure 1 The diagram shows the structure of a typical perfluorinated compound (perfluorooctanoic acid). Its molecular structure contains stable carbon-fluorine bonds, which is the core reason why PFCs are difficult to remove using traditional methods. The molecule contains a perfluoroalkyl carbon chain and a carboxyl group. The high bond energy and stability of the carbon-fluorine bonds within the molecule are key reasons why perfluorinated compounds are difficult to degrade and remove using traditional methods. This structure is also an important reference for the design of the solid-phase extraction matrix in this invention. In summary, currently, there is no effective treatment device on the market for removing PFCs from mobile phase pure water. Conventional pure water machines use the principle of ion exchange, which can only effectively remove inorganic fluorides from water, and the removal effect on fluorinated organic compounds is not ideal. Commercially available pure water is mostly packaged in plastic, and its PFC background value is unknown. Laboratories need to purchase different batches and brands of pure water for background measurements before use, which has the disadvantages of high uncertainty and large workload. Summary of the Invention

[0006] The purpose of this invention is to overcome the shortcomings of existing technologies and address the problems in related technologies by providing a pretreatment device for removing PFCs from laboratory water. Through a rational internal and external structural design, novel PFC purification materials are filled into the purification device, integrating purification, water intake, and water storage functions. This device can conveniently and quickly meet the needs of laboratory PFC detection and analysis, ensuring the accuracy of test results. It is also simple to use and low in cost, providing technical support for the efficient and high-quality completion of PFC detection in water, food, and biological samples.

[0007] The first aspect of the present invention is to provide an apparatus for removing perfluorinated and polyfluorinated organic compounds from experimental water, comprising a water inlet (1), a purification device (2), a water storage tank (3), and an external protective shell (4); the water inlet (1), the purification device (2), and the water storage tank (3) are sequentially fixed inside the external protective shell (4) and are fluidly connected by a pipe;

[0008] The water inlet device (1) includes an inlet connector (101), a water flow stabilizer (102), and a peristaltic pump (103). The three components are connected in sequence to form a complete water inlet passage. Pure water produced by the laboratory pure water machine enters the interior of the water inlet device (1) through the inlet connector (101). Under the action of the water flow stabilizer (102), it is pumped into the purification device (2) at a uniform speed by the peristaltic pump (103). The water flow stabilizer (102) is used to avoid fluctuations in the water flow rate, ensure stable contact time between pure water and solid phase extraction matrix, and improve the purification effect. The peristaltic pump (103) is used to precisely control the water inlet speed to adapt to different purification needs.

[0009] The purification device (2) includes a stainless steel mesh screen (201), a solid phase extraction matrix (202), a pipe connector (204), an outlet connector pipe (205), and a support structure (206). The internal components of the purification device (2) are arranged sequentially from top to bottom as follows: pipe connector (204), solid phase extraction matrix (202), stainless steel mesh screen (201), support structure (206), and outlet connector pipe (205). The stainless steel mesh screen (201) serves to support the solid phase extraction matrix (202). To prevent the substrate from being lost with the water flow; the outlet connector pipe (205) is connected to the inlet (301) of the water storage tank (3) to realize the transportation of purified water; after the pure water flows in from the water inlet (1), it enters the purification device (2) through the pipe connector (204); after the water is purified by the solid phase extraction substrate (202) of the purification device (2), it enters the water storage tank (3) through the outlet connector pipe (205); a stainless steel support structure (206) is set inside the outer shell to fix and support the internal membrane and substrate;

[0010] The water storage tank (3) includes an inlet (301), an ultraviolet lamp (302), and an outlet (303); the inlet (301) is provided on the upper part of the side wall of the tank and is connected to the outlet connector pipe (205) of the purification device (2) by a thread; the ultraviolet lamp (302) is built into the top of the water storage tank (3) for periodically sterilizing the pure water inside the water storage tank (3); the outlet (303) is provided on the lower part of the side wall for taking out the purified pure water.

[0011] The outer protective shell (4) is used to fix the water inlet (1), the purification device (2) and the water storage tank (3), and to protect the internal components. The outer protective shell (4) has a window-type opening (401) on the front of the shell body, and a sealing cover is provided at the opening to facilitate the replacement of the solid phase extraction matrix (202) in the purification device (2). The right side of the shell body opening is also provided with a peristaltic pump start / stop button (402), which is electrically connected to the peristaltic pump (103) of the water inlet (1) to control the water inlet process.

[0012] Preferably, the inlet connector (101) is made of polypropylene and is compatible with the outlet of the laboratory pure water machine.

[0013] Preferably, the water flow stabilizer (102) is provided with guide vanes inside to buffer the inlet water pressure and stabilize the water flow velocity.

[0014] Preferably, the peristaltic pump (103) has a stainless steel casing and is equipped with an adjustable speed motor to achieve precise control of the water inlet speed.

[0015] Preferably, the purification device (2) is a cylindrical structure made of stainless steel; the stainless steel mesh screen plate (201) is a stainless steel mesh screen plate (201) with a pore size of 2μm; the pipe connector (204) is a double-layer embedded structure made of stainless steel, which is convenient to connect with the water outlet pipe of the water inlet (1); the support structure (206) is a hollow bracket made of stainless steel, which enhances the structural stability of the device.

[0016] Preferably, the water storage tank (3) is a sealed tank made of 316 stainless steel; a 185 / 254nm dual-wavelength ultraviolet lamp (302) is built into the top of the tank and the ultraviolet lamp is fixed by a bracket; and an anti-slip pad is provided at the bottom of the sealed tank.

[0017] Preferably, the upper side of the outer protective housing (4) is equipped with a handle (403) and the bottom is equipped with two pulleys (404). The outer protective housing (4) is made of hard plastic. The interior of the outer protective housing (4) is provided with slots and brackets for fixing the water inlet (1), the purification device (2) and the water storage device (3).

[0018] Preferably, the solid-phase extraction matrix (202) has the ability to selectively adsorb PFCs and is used to selectively adsorb fluorinated organic compounds; wherein, the main body of the solid-phase extraction matrix (202) is a porous polymer microsphere formed by copolymerization of divinylbenzene and glycidyl methacrylate; the porous polymer microsphere has a pore volume of 0.2~0.6cc / g, a particle size of 10~80μm, and a specific surface area of ​​100~300m² / g, possessing a large adsorption capacity and adsorption sites, providing sufficient space for the adsorption of PFCs; the surface of the porous polymer microsphere is covered with a perfluoroalkyl derivatization layer, which is formed by reacting the perfluoroalkyl derivatization layer with the epoxy groups on the surface of the porous polymer microsphere through any one or more perfluoroderivatizing reagents selected from perfluoroalcohols, perfluorothiols, and perfluorocarboxylic acids; the carbon chain length of the perfluoroalkyl derivatization layer is C6 to C12, and it covers at least 70% of the surface formed by the porous polymer microsphere.

[0019] Preferably, the perfluorinated derivatizing reagent includes one or more of perfluorohexylethanol, perfluorooctylethanol, fluorohexylethanethiol, perfluorooctylethanethiol, 1H,1H,2H,2H-perfluorododecanethiol, perfluorohexanoic acid, perfluorooctanoic acid, and perfluorodecanoic acid.

[0020] A second aspect of the present invention provides a method for purifying experimental water based on the apparatus of the first aspect, comprising:

[0021] S1, Matrix loading: Open the window opening (401) of the outer protective shell (4), load the solid phase extraction matrix (202) onto the stainless steel mesh screen plate (201) of the purification device (2) to ensure uniform distribution of the matrix; tighten the threaded sealing structure of the purification device (2) to ensure the device is airtight.

[0022] S2, Device connection: Connect the inlet connector (101) of the water inlet (1) tightly to the outlet of the laboratory pure water machine; check the pipe connection between the purification device (2) and the water storage device (3) to confirm that the connection is sealed and there is no leakage;

[0023] S3, Pure water purification: Press the peristaltic pump start button (402) on the outer protective shell (4), and the peristaltic pump (103) starts; after the flow rate of the water produced by the laboratory pure water machine is stabilized by the water flow stabilizer (102), it is pumped into the purification device (2) at a uniform speed; the pure water is in full contact with the solid phase extraction matrix (202) in the purification device (2), and the perfluorinated and polyfluorinated organic compounds in the water are selectively adsorbed by the matrix; the purified pure water flows into the water storage tank (3) through the outlet connector pipe (205).

[0024] S4, Pure water storage and use: The ultraviolet lamp (302) on the top of the water storage device (3) is turned on at regular intervals to sterilize the stored pure water and prevent bacterial growth; when the laboratory needs to use the purified pure water, it can be taken directly by opening the outlet (303) of the water storage device (3).

[0025] The beneficial effects of the device of the present invention:

[0026] 1. Fills a market gap and has a wide range of applications.

[0027] Currently, there are no similar products on the market. This device achieves highly efficient removal of PFCs based on a unique solid-phase extraction matrix. It can be used with various types of pure water systems in laboratories, without being limited by the brand or model of the pure water system, making it widely applicable.

[0028] 2. Significant removal effect, ensuring accurate detection.

[0029] After treatment with this device, the content of perfluorinated and polyfluorinated organic compounds (PFCs) in experimental pure water can be reduced to below 1 ng / L. This effect provides technical support for the accurate and effective detection of PFCs in various matrix samples, and significantly enhances the laboratory quality control level of PFC detection.

[0030] 3. No secondary pollution, ensuring the purity of pure water.

[0031] The core components of the device are made of stable materials such as polypropylene, stainless steel, and 316 stainless steel. The solid phase extraction matrix selectively adsorbs PFCs only and will not introduce other impurities into the pure water, thus avoiding secondary pollution and ensuring the purity of the pure water.

[0032] 4. Low cost and easy operation

[0033] The raw materials for preparing solid-phase extraction matrices are readily available and inexpensive. The device is easy to operate, requiring only a button to start and stop the peristaltic pump, and matrix replacement can be done by simply opening the window opening. No professional personnel are required, reducing the barrier to entry and maintenance costs for laboratories.

[0034] 5. High degree of integration, meeting the requirements for large volume.

[0035] This device integrates purification, water storage, and sterilization functions, and can quickly prepare experimental water without PFCs. The water storage unit (3) can store a large amount of purified pure water, which can meet the needs of the laboratory for large volumes of pure water and improve experimental efficiency. Attached Figure Description

[0036] To more clearly illustrate the technical solutions in the specific embodiments or related technologies of the present invention, the drawings used in the description of the specific embodiments or related technologies will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0037] Figure 1 The diagram shows the structure of a typical perfluorinated compound (perfluorooctanoic acid);

[0038] Figure 2 This is a schematic diagram of the device for removing perfluorinated and polyfluorinated organic compounds from experimental water according to an embodiment of the present invention;

[0039] Figure 3 This is a schematic diagram of the water inlet structure provided in an embodiment of the present invention;

[0040] Figure 4 This is a schematic diagram of the purification device provided in an embodiment of the present invention;

[0041] Figure 5 A schematic diagram of the water storage device structure provided in an embodiment of the present invention;

[0042] Figure 6 The UPLC-MS / MS detection spectrum is provided for the experiment in the embodiment of the present invention.

[0043] Reference numerals: 1-Water inlet; 101-Inlet connector; 102-Flow stabilizer; 103-Peristaltic pump; 2-Purification device; 201-Stainless steel mesh screen; 202-Solid phase extraction matrix; 204-Pipe connector; 205-Outlet connector pipe; 206-Stainless steel support structure; 3-Water reservoir; 301-Inlet; 302-Dual-wavelength ultraviolet lamp; 303-Outlet; 4-External protective housing; 401-Window opening; 402-Peristaltic pump start / stop button; 403-Handle; 404-Pulley. Detailed Implementation

[0044] The technical solution of the present invention will now be clearly and completely described with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0045] In the description of this invention, it should be noted that the terms "center," "upper," "lower," "left," "right," "vertical," "horizontal," "inner," and "outer," etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are used only for the convenience of describing the invention and for 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. Therefore, they should not be construed as limitations on the invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and should not be construed as indicating or implying relative importance.

[0046] 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 can understand the specific meaning of the above terms in this invention based on the specific circumstances.

[0047] The term “about” is used here in conjunction with numerical values ​​to include normal variation in measurements as expected by those skilled in the art, and should be understood to have the same meaning as “approximately” and to cover typical error margins, such as ±5% of the specified value.

[0048] Terms such as “one,” “an,” and “the” are not intended to refer to a single entity, but rather to include general categories that can be illustrated using specific examples.

[0049] Unless otherwise stated, any amount (e.g., concentration) of a component in a composition given as a percentage (%) refers to a weight percentage per volume.

[0050] Example 1

[0051] like Figure 2 As shown, a device for removing perfluorinated and polyfluorinated organic compounds from experimental water includes four functional components: a water inlet (1), a purification device (2), a water storage tank (3), and an external protective shell (4). The water inlet (1), purification device (2), and water storage tank (3) are sequentially fixed inside the external protective shell (4) and connected by pipes. The overall structure is compact, highly integrated, and combines practicality and convenience.

[0052] The water inlet (1) is made of polypropylene and stainless steel and includes an inlet connector (101), a water flow stabilizer (102), and a peristaltic pump (103). Pure water produced by the laboratory pure water machine enters the interior of the water inlet through the inlet connector (101) and is pumped into the purification device (2) at a uniform speed by the peristaltic pump (103) under the action of the water flow stabilizer (102). The water flow stabilizer (102) is used to avoid fluctuations in the inlet flow rate, ensure stable contact time between pure water and solid phase extraction matrix, and improve the purification effect. The peristaltic pump (103) is used to precisely control the inlet speed and adapt to different purification needs.

[0053] In this embodiment, Figure 3 The diagram shows the structure of the water inlet device (1) of this invention. The water inlet device includes an inlet connector (101), a water flow stabilizer (102), and a peristaltic pump (103). The inlet connector (101) is made of polypropylene and is compatible with the outlet of a laboratory pure water machine. The water flow stabilizer (102) has guide vanes inside to buffer the inlet water pressure and stabilize the water flow speed. The peristaltic pump (103) has a stainless steel shell and is equipped with an adjustable motor to achieve precise control of the inlet water speed. The three components are connected in sequence to form a complete water inlet passage. The inlet connector (101) and the water flow stabilizer (102) of the water inlet device (1) are manufactured using injection molding. The peristaltic pump (103) is purchased from a laboratory equipment company.

[0054] The purification device (2) is a cylindrical structure made of stainless steel, which is sealed by threaded connection and has good sealing performance. It includes a stainless steel mesh screen plate (201), a solid phase extraction matrix (202), a pipe connector (204), an outlet connector pipe (205), and a support structure (206). The purification device (2) is equipped with a stainless steel mesh screen plate (201) with a pore size of 2μm, which supports the solid phase extraction matrix (202) and prevents the matrix from being lost with the water flow. After pure water flows in from the inlet (1), it enters the purification device (2) through the stainless steel double-layer embedded structure pipe connector (204). The double-layer embedded structure facilitates disassembly and maintenance. After the water is purified by the solid phase extraction matrix (202) of the purification device (2), it enters the water storage tank (3) through the outlet connector pipe (205). The purification device has a cylindrical shell, and a stainless steel support structure (206) is set inside the shell to fix and support the internal membrane and matrix, thereby improving the structural stability of the device.

[0055] In this embodiment, Figure 4This is a schematic diagram of the purification device (2), which is a cylindrical structure made of stainless steel. The device is arranged from top to bottom as follows: pipe connector (204), solid-phase extraction matrix (202), stainless steel mesh screen (201), support structure (206), and outlet connector pipe (205). The pipe connector (204) has a double-layered embedded structure, facilitating connection to the outlet pipe of the inlet device (1); the stainless steel mesh screen (201) has a 2μm aperture and is used to support the solid-phase extraction matrix (202); the support structure (206) is a stainless steel hollow bracket, enhancing the structural stability of the device; the outlet connector pipe (205) connects to the inlet (301) of the water storage device (3) to achieve the delivery of purified water. The upper and lower ends of the device are sealed with threads to ensure the device's airtightness. The cylindrical shell, stainless steel mesh screen plate (201), pipe connectors (204) and support structure (206) of the purification device (2) are made by precision casting and machining; the solid phase extraction matrix (202) is custom-synthesized by a materials technology company.

[0056] The water storage device (3) is made of 316 stainless steel, which has good corrosion resistance and stability and will not introduce impurities into the pure water. The water storage device (3) includes an inlet (301), an ultraviolet lamp (302) and an outlet (303). The inlet (301) is tightly connected to the outlet pipe of the purification device (2) through a threaded device to ensure the connection is sealed and prevent external pollution. The top of the water storage device (3) has a built-in 185 / 254nm dual-wavelength ultraviolet lamp (302) for periodically sterilizing the pure water inside the water storage device (3) to prevent bacteria from growing during the storage of pure water. When taking water, simply open the outlet (303) for convenient operation.

[0057] In this embodiment, Figure 5 This is a structural diagram of the water storage tank (3), which is a sealed tank made of 316 stainless steel. A 185 / 254nm dual-wavelength ultraviolet lamp (302) is built into the top of the tank and fixed by a bracket, enabling 360° sterilization without dead angles. An inlet (301) is located on the upper side wall of the tank, connected to the outlet pipe (205) of the purification device (2) via threads; an outlet (303) is located on the lower side wall for taking purified water. Anti-slip pads are installed at the bottom of the tank to enhance the stability of the water storage tank. The water storage tank (3) is welded from 316 stainless steel plates by a stainless steel products company; the 185 / 254nm dual-wavelength ultraviolet lamp (302) on top is purchased from an ultraviolet equipment company.

[0058] The outer protective shell (4) is used to fix the water inlet (1), the purification device (2) and the water storage device (3), and to protect the internal components. The outer protective shell (4) has a window-type opening (401) to facilitate the replacement of the solid phase extraction matrix (202) in the purification device (2). The shell is also equipped with a peristaltic pump start / stop button (402) to control the water inlet process. The upper side of the outer protective shell (4) is equipped with a handle (403) and the bottom is equipped with two pulleys (404) to facilitate the overall movement of the device and improve the flexibility and practicality of the device.

[0059] In this embodiment, Figure 2 The middle section illustrates the structure of the outer protective shell (4), which is made of hard plastic and has good protective performance. A window-type opening (401) is provided on the front of the shell, and a sealing cover is provided at the opening to facilitate the replacement of the solid phase extraction matrix (202) of the purification device (2). A peristaltic pump start / stop button (402) is provided on the right side of the opening, which is electrically connected to the peristaltic pump (103) of the water inlet (1). Handles (403) are provided on both sides of the upper part of the shell for easy handling of the device; two pulleys (404) are provided at the bottom to improve the ease of movement of the device. The shell is equipped with slots and brackets for fixing the water inlet (1), the purification device (2) and the water tank (3). The outer protective shell (4) is manufactured by a mold manufacturing company using injection molding process; the handles (403) and pulleys (404) are purchased from a hardware accessories company.

[0060] As a preferred embodiment, the core material in the purification device (2) is a solid-phase extraction matrix (202), which has the ability to selectively adsorb PFCs and is used to selectively adsorb fluorine-containing organic compounds. The solid-phase extraction matrix (202) is mainly composed of porous polymer microspheres formed by copolymerization of divinylbenzene and glycidyl methacrylate. The porous polymer microspheres have a pore volume of 0.2~0.6cc / g, a particle size of 10~80μm, and a specific surface area of ​​100~300m² / g, which provides a large adsorption capacity and adsorption sites, providing sufficient space for the adsorption of PFCs. The surface of the porous polymer microspheres is covered with a perfluoroalkyl derivatization layer, which is formed by reacting the epoxy groups on the surface of the porous polymer microspheres with any one or more perfluoroderivatizing reagents selected from perfluoroalcohols, perfluorothiols, and perfluorocarboxylic acids. The carbon chain length of the perfluoroalkyl derivatization layer is C6 to C12, and it covers at least 70% of the surface formed by the porous polymer microspheres.

[0061] In a preferred embodiment, the perfluorinated derivatizing agent includes one or more of perfluorohexylethanol, perfluorooctylethanol, fluorohexylethanethiol, perfluorooctylethanethiol, 1H,1H,2H,2H-perfluorododecanethiol, perfluorohexanoic acid, perfluorooctanoic acid, and perfluorodecanoic acid. By selecting different types of derivatizing agents, the removal requirements of different types of PFCs can be met.

[0062] In this embodiment, the core function of the solid-phase extraction matrix (202) is to selectively adsorb fluorinated organic compounds. The principle is that there is a hydrophobic interaction and fluorine-fluorine interaction between the perfluoroalkyl derivatized layer and PFCs, which can efficiently identify and capture PFCs in water, thereby purifying the experimental water.

[0063] Example 2

[0064] This embodiment provides a method for purifying experimental water based on the device of Embodiment 1, including:

[0065] S1, Matrix loading: Open the window opening (401) of the outer protective shell (4), load the solid phase extraction matrix (202) onto the stainless steel mesh screen plate (201) of the purification device (2) to ensure uniform distribution of the matrix; tighten the threaded sealing structure of the purification device (2) to ensure the device is airtight.

[0066] S2, Device connection: Connect the inlet connector (101) of the water inlet (1) tightly to the outlet of the laboratory pure water machine; check the pipe connection between the purification device (2) and the water storage device (3) to confirm that the connection is sealed and there is no leakage;

[0067] S3, Pure water purification: Press the peristaltic pump start button (402) on the outer protective shell (4), and the peristaltic pump (103) starts; after the flow rate of the water produced by the laboratory pure water machine is stabilized by the water flow stabilizer (102), it is pumped into the purification device (2) at a uniform speed; the pure water is in full contact with the solid phase extraction matrix (202) in the purification device (2), and the perfluorinated and polyfluorinated organic compounds in the water are selectively adsorbed by the matrix; the purified pure water flows into the water storage tank (3) through the outlet connector pipe (205).

[0068] S4, Pure water storage and use: The 185 / 254nm dual-wavelength ultraviolet lamp (302) on the top of the water storage tank (3) is turned on at regular intervals to sterilize the stored pure water and prevent bacterial growth; when the laboratory needs to use purified pure water, it can be taken directly by opening the outlet (303) of the water storage tank (3).

[0069] (I) Application Example 1: Experiment on PFC Removal from Simulated Polluted Pure Water

[0070] 1. Device component parameters

[0071] Water inlet 1: The diameter of the inlet connector 101 is 10mm; the number of guide vanes of the water flow stabilizer 102 is 6; the speed adjustment range of the peristaltic pump 103 is 0~100r / min, and in this embodiment the speed is set to 50r / min, and the corresponding water flow rate is 50mL / min.

[0072] Purification device 2: The inner diameter of the cylindrical structure is 50 mm and the height is 200 mm; the pore size of the stainless steel mesh screen plate 201 is 2 μm; the parameters of the solid phase extraction matrix 202 are: pore volume of porous polymer microspheres 0.4 cc / g, particle size 50 μm, specific surface area 200 m² / g; the carbon chain length of the perfluoroalkyl derivatization layer is C12, the derivatization reagent is 1H,1H,2H,2H-perfluorododecylthiol, and the derivatization layer covers 85% of the surface of the polymer microspheres; the matrix loading is 100 g.

[0073] Water storage tank 3: volume is 10L; UV lamp 302 power is 30W, sterilization time is set to turn on for 30 minutes every 2 hours.

[0074] External protective housing 4: dimensions are 50cm long × 30cm wide × 80cm high; window opening 401 has dimensions of 20cm long × 15cm wide; pulley 404 has a load-bearing capacity of 50kg.

[0075] 2. Experimental Procedure

[0076] S1, Preparation of simulated contaminated pure water: Forty perfluorinated and polyfluorinated organic standard samples, each with a concentration of 10 ng / L, were added to the water produced by a laboratory pure water machine to prepare simulated contaminated pure water for subsequent removal experiments.

[0077] S2, Device Preparation: Open the window opening 401 of the outer protective housing 4, and evenly fill 100g of solid phase extraction matrix 202 onto the stainless steel mesh screen plate 201 of the purification device 2. Tighten the threaded sealing cap of the purification device 2. Connect the inlet connector 101 of the water inlet 1 to the outlet of the laboratory pure water machine, and confirm that the pipe connection between the purification device 2 and the water storage tank 3 is sealed.

[0078] S3, Pure Water Purification: Press the peristaltic pump start button 402. The peristaltic pump 103 runs at a speed of 50 r / min, pumping simulated contaminated pure water into the purification device 2 at a uniform speed. The pure water comes into full contact with the solid phase extraction matrix 202 in the purification device 2 for 2 minutes, and then flows into the water storage tank 3.

[0079] S4, Detection and Analysis: Simulated contaminated pure water samples before and after purification were collected and analyzed using ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS / MS). Detection conditions were as follows: C18 column, 100 mm × 2.1 mm, 1.7 μm; mobile phase, methanol-water (80:20 v / v); flow rate, 0.3 mL / min; column temperature, 30 °C; injection volume, 10 μL; mass spectrometry was performed in electrospray ionization negative ion mode with multiple reaction monitoring (MRM) scanning.

[0080] (ii) Comparative Example 1

[0081] Water produced by a conventional laboratory pure water system (without being purified by the device of this invention) was used as a control sample. No PFCs standards were added, and the same UPLC-MS / MS detection conditions were used to analyze the background content of PFCs.

[0082] 1. Results Comparison and Analysis

[0083] (1) Spectral comparison analysis

[0084] like Figure 6 As shown, the UPLC-MS / MS detection spectra of this experiment are divided into left and right sides. The left side is the spectrum of the untreated simulated contaminated pure water sample, and the right side is the spectrum of the pure water sample treated by the device of this invention. In the spectrum of the simulated contaminated pure water on the left, obvious characteristic peaks appear at the retention times corresponding to the 40 PFCs, with large peak heights and peak areas, indicating a high content of PFCs in the water. For example, the retention time of perfluoropentanesulfonic acid is about 9.3 min, and its characteristic peak height is 100 mV; the retention time of perfluorooctanesulfonic acid is about 9.8 min, and its characteristic peak height is 95 mV. In the spectrum of the pure water treated by this device on the right, at the same retention time, the original characteristic peaks are significantly reduced, and the characteristic peaks corresponding to some PFCs even disappear completely. For example, the peak height of the characteristic peak corresponding to perfluoropentanesulfonic acid drops to below 1 mV; the peak height of the characteristic peak corresponding to perfluorooctanesulfonic acid drops to below 0.5 mV, indicating that the PFCs in the water are efficiently removed.

[0085] (2) Data comparison and analysis: The PFCs content detection results of Example 1 and Comparative Example 1 are compared in Table 1.

[0086] Table 1

[0087]

[0088] As shown in Table 1, the simulated contaminated pure water treated by the device of this invention had an average content of 40 PFCs of only 0.3 ng / L, with the highest content not exceeding 0.8 ng / L and the lowest content being 0.05 ng / L, all below the target value of 1 ng / L. In contrast, 12 PFCs were detected in the product water of a conventional pure water machine, with an average content of 2.5 ng / L and a highest content reaching 5.2 ng / L, which fails to meet the laboratory quality control requirements.

[0089] In summary, the device of the present invention has a significant removal effect on PFCs in simulated polluted pure water, effectively reducing the PFC content in the water and ensuring the purity of the experimental water.

[0090] (III) Application Example 2: PFC Removal Experiments in Laboratory Pure Water from Different Regions

[0091] 1. Device component parameters: The device component parameters are exactly the same as those in Application Example 1, and the loading amount of solid phase extraction matrix 202 is still 100g.

[0092] 2. Experimental Procedure

[0093] S1, Sample Collection: Water samples from pure water machines were collected from laboratories in three different regions and labeled as Sample A, Sample B, and Sample C. The levels of PFC contamination varied among the three regions. Sample A was collected from a region with high PFC contamination, Sample B from a region with moderate contamination, and Sample C from a region with low contamination.

[0094] S2, Device preparation: Complete the loading and connection of the device according to the steps of Example 1.

[0095] S3, Pure water purification: Press the peristaltic pump start button 402 to pump the three samples into the purification device 2 for purification. The inlet flow rate is set to 50 mL / min, the contact time is 2 min, and the purified pure water is stored in the water storage tank 3.

[0096] S4, Detection and Analysis: Collect pure water samples before and after purification for three samples respectively, and analyze them using the same UPLC-MS / MS detection conditions as in Application Example 1. Calculate the total content of PFCs in each sample.

[0097] (iv) Comparative Example 2

[0098] A commercially available brand of bottled purified water was used as a control sample, labeled as sample D. The PFC content in sample D was analyzed by UPLC-MS / MS.

[0099] 1. Results Comparison and Analysis: Table 2 shows the comparison of the total PFC content of laboratory pure water before and after purification and commercially available bottled pure water in different regions.

[0100] Table 2

[0101]

[0102] As shown in Table 2, the device of this invention has a significant PFC removal effect on laboratory pure water from areas with different levels of pollution, with a removal rate of over 93%. Specifically, the total PFC content after purification is 0.7 ng / L in highly polluted areas, 0.4 ng / L in moderately polluted areas, and 0.2 ng / L in low-polluted areas, all below 1 ng / L. In contrast, the total PFC content in commercially available bottled pure water is 3.5 ng / L, which cannot meet the quality control requirements for laboratory testing.

[0103] The experimental results show that the device of the present invention can be adapted to the purification of experimental water with different levels of pollution, and has wide applicability and stable removal effect.

[0104] The working principle of the device for removing perfluorinated and polyfluorinated organic compounds from experimental water according to the present invention mainly includes three core parts: the principle of steady influent flow, the principle of selective adsorption, and the principle of pure water storage and sterilization.

[0105] 1. Inlet water flow stabilization principle

[0106] The water produced by the laboratory pure water system enters the inlet device (1) through the inlet connector (101) and first flows through the flow stabilizer (102). The guide vanes inside the flow stabilizer (102) can buffer the inlet water pressure, eliminate water flow fluctuations, and keep the water flow at a stable speed and direction. Then, the peristaltic pump (103) runs at a set speed to pump the stabilized pure water into the purification device (2) at a uniform speed. This process can ensure that the contact time between the pure water and the solid phase extraction matrix (202) is consistent, avoid the instability of the purification effect caused by flow fluctuations, and lay the foundation for efficient removal of PFCs.

[0107] 2. Selective adsorption principle

[0108] This is the core working principle of the device of the present invention. When pure water enters the purification device (2), it comes into full contact with the solid phase extraction matrix (202). The solid phase extraction matrix (202) is composed of porous polymer microspheres and a perfluoroalkyl derivatized layer.

[0109] (1) Porous polymer microspheres have a large specific surface area and pore volume, providing sufficient physical space for the adsorption of PFCs and can accommodate a large number of PFC molecules.

[0110] (2) The perfluoroalkyl derivatized layer on the surface of the polymer microspheres contains carbon-fluorine bonds in its molecular structure. When PFC molecules come into contact with the derivatized layer, fluorine-fluorine interactions and hydrophobic interactions occur. The fluorine-fluorine interaction refers to the attractive force between fluorine atoms in the derivatized layer and fluorine atoms in the PFC molecules; the hydrophobic interaction refers to the interaction between the hydrophobicity of the derivatized layer and the hydrophobicity of the PFC molecules.

[0111] (3) Under the combined action of the two forces, PFC molecules are efficiently recognized and captured, and adsorbed on the surface of the solid phase extraction matrix (202). Other harmless components in the pure water are not adsorbed and can pass smoothly through the purification device (2), thereby achieving selective removal of PFCs.

[0112] 3. Principle of pure water storage and sterilization

[0113] The purified water, after PFCs are removed by the purification device (2), flows into the water storage tank (3) for storage. The 185 / 254nm dual-wavelength ultraviolet lamp (302) built into the top of the water storage tank (3) is turned on at regular intervals. The 185nm wavelength ultraviolet light can convert oxygen in the water into ozone, which has strong oxidizing properties and can kill bacteria; the 254nm wavelength ultraviolet light can directly destroy the DNA structure of bacteria, achieving a sterilization effect. The two wavelengths of ultraviolet light work together to completely sterilize the purified water in the water storage tank, prevent bacteria from growing in the purified water during storage, and ensure the sterility and purity of the experimental water. When the laboratory needs water, it can be directly used by opening the water outlet (303), which is convenient and efficient.

[0114] This invention discloses a device for removing perfluorinated and polyfluorinated organic compounds from laboratory water. It integrates functions such as stabilizing influent flow, selective adsorption, and water storage sterilization. It has the advantages of significant removal effect, no secondary pollution, simple operation, and wide applicability.

[0115] This device can be widely used in environmental monitoring laboratories, food safety testing laboratories, and biomedical research and development laboratories to provide high-quality laboratory water for the detection and analysis of PFCs. Simultaneously, it can also be used in conjunction with various pure water systems to solve the technical challenge of existing pure water preparation methods failing to effectively remove PFCs.

[0116] With increasingly stringent PFC pollution controls in various countries, the demand for laboratory water with low PFC background levels will continue to grow. The device of this invention has broad market application prospects, providing reliable technical support for laboratory quality control in PFC detection, and possesses significant economic and social value.

[0117] Through the above description of the embodiments, those skilled in the art can clearly understand that the above embodiments can be implemented by software, or by using software plus necessary general-purpose hardware platforms. Based on this understanding, the technical solutions of the above embodiments can be embodied in the form of a software product, which can be stored in a non-volatile storage medium (such as a CD-ROM, USB flash drive, mobile hard drive, etc.), including several instructions to cause a computer device (such as a personal computer, server, or network device, etc.) to execute the methods described in the various embodiments of the present invention.

[0118] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. An apparatus for removing perfluorinated and polyfluorinated organic compounds from laboratory water, characterized in that, It includes a water inlet (1), a purification device (2), a water storage tank (3), and an outer protective shell (4); the water inlet (1), the purification device (2), and the water storage tank (3) are fixed inside the outer protective shell (4) in sequence and are connected by a pipe; The water inlet device (1) includes an inlet connector (101), a water flow stabilizer (102), and a peristaltic pump (103). The three components are connected in sequence to form a complete water inlet passage. Pure water produced by the laboratory pure water machine enters the interior of the water inlet device (1) through the inlet connector (101). Under the action of the water flow stabilizer (102), it is pumped into the purification device (2) at a uniform speed by the peristaltic pump (103). The water flow stabilizer (102) is used to avoid fluctuations in the water flow rate, ensure stable contact time between pure water and solid phase extraction matrix, and improve the purification effect. The peristaltic pump (103) is used to precisely control the water inlet speed to adapt to different purification needs. The purification device (2) includes a stainless steel mesh screen (201), a solid phase extraction matrix (202), a pipe connector (204), an outlet connector pipe (205), and a support structure (206). The internal components of the purification device (2) are arranged sequentially from top to bottom as follows: pipe connector (204), solid phase extraction matrix (202), stainless steel mesh screen (201), support structure (206), and outlet connector pipe (205). The stainless steel mesh screen (201) serves to support the solid phase extraction matrix (202). To prevent the substrate from being lost with the water flow; the outlet connector pipe (205) is connected to the inlet (301) of the water storage tank (3) to realize the transportation of purified water; after the pure water flows in from the water inlet (1), it enters the purification device (2) through the pipe connector (204); after the water is purified by the solid phase extraction substrate (202) of the purification device (2), it enters the water storage tank (3) through the outlet connector pipe (205); a stainless steel support structure (206) is set inside the outer shell to fix and support the internal membrane and substrate; The water storage tank (3) includes an inlet (301), an ultraviolet lamp (302), and an outlet (303); the inlet (301) is provided on the upper part of the side wall of the tank and is connected to the outlet connector pipe (205) of the purification device (2) by a thread; the ultraviolet lamp (302) is built into the top of the water storage tank (3) for periodically sterilizing the pure water inside the water storage tank (3); the outlet (303) is provided on the lower part of the side wall for taking out the purified pure water. The outer protective shell (4) is used to fix the water inlet (1), the purification device (2) and the water storage tank (3), and to protect the internal components. The outer protective shell (4) has a window-type opening (401) on the front of the shell body, and a sealing cover is provided at the opening to facilitate the replacement of the solid phase extraction matrix (202) in the purification device (2). The right side of the shell body opening is also provided with a peristaltic pump start / stop button (402), which is electrically connected to the peristaltic pump (103) of the water inlet (1) to control the water inlet process.

2. The apparatus for removing perfluorinated and polyfluorinated organic compounds from experimental water according to claim 1, characterized in that, The inlet connector (101) is made of polypropylene and is compatible with the outlet of the laboratory pure water machine.

3. The apparatus for removing perfluorinated and polyfluorinated organic compounds from experimental water according to claim 2, characterized in that, The water flow stabilizer (102) is equipped with guide vanes to buffer the inlet water pressure and stabilize the water flow velocity.

4. The apparatus for removing perfluorinated and polyfluorinated organic compounds from experimental water according to claim 3, characterized in that, The peristaltic pump (103) has a stainless steel casing and is equipped with an adjustable speed motor to achieve precise control of the water inlet speed.

5. The apparatus for removing perfluorinated and polyfluorinated organic compounds from experimental water according to claim 4, characterized in that, The purification device (2) is a cylindrical structure made of stainless steel; the stainless steel mesh screen plate (201) is a stainless steel mesh screen plate (201) with a pore size of 2μm; the pipe connector (204) is a double-layer embedded structure made of stainless steel, which is convenient to connect with the outlet pipe of the water inlet (1); the support structure (206) is a hollow bracket made of stainless steel, which enhances the structural stability of the device.

6. The apparatus for removing perfluorinated and polyfluorinated organic compounds from experimental water according to claim 5, characterized in that, The water storage tank (3) is a sealed tank made of 316 stainless steel; a 185 / 254nm dual-wavelength ultraviolet lamp (302) is built into the top of the tank and the ultraviolet lamp is fixed by a bracket; an anti-slip pad is provided at the bottom of the sealed tank.

7. The apparatus for removing perfluorinated and polyfluorinated organic compounds from experimental water according to claim 6, characterized in that, The upper side of the outer protective housing (4) is equipped with a handle (403) and the bottom is equipped with two pulleys (404). The outer protective housing (4) is made of hard plastic. The interior of the outer protective housing (4) is provided with slots and brackets for fixing the water inlet (1), the purification device (2) and the water storage device (3).

8. The apparatus for removing perfluorinated and polyfluorinated organic compounds from experimental water according to claim 7, characterized in that, The solid-phase extraction matrix (202) has the ability to selectively adsorb PFCs and is used to selectively adsorb fluorinated organic compounds. The solid-phase extraction matrix (202) is mainly composed of porous polymer microspheres formed by copolymerization of divinylbenzene and glycidyl methacrylate. The porous polymer microspheres have a pore volume of 0.2~0.6cc / g, a particle size of 10~80μm, and a specific surface area of ​​100~300m² / g, which provides a large adsorption capacity and adsorption sites, providing sufficient space for the adsorption of PFCs. The surface of the porous polymer microspheres is covered with a perfluoroalkyl derivatization layer, which is formed by reacting the perfluoroalkyl derivatization layer with the epoxy groups on the surface of the porous polymer microspheres through any one or more perfluoroderivatizing reagents selected from perfluoroalcohols, perfluorothiols, and perfluorocarboxylic acids. The carbon chain length of the perfluoroalkyl derivatization layer is C6 to C12, and it covers at least 70% of the surface formed by the porous polymer microspheres.

9. The apparatus for removing perfluorinated and polyfluorinated organic compounds from experimental water according to claim 8, characterized in that, The perfluorinated derivatizing reagent includes one or more of the following: perfluorohexylethanol, perfluorooctylethanol, fluorohexylethanethiol, perfluorooctylethanethiol, 1H,1H,2H,2H-perfluorododecanethiol, perfluorohexanoic acid, perfluorooctanoic acid, and perfluorodecanoic acid.

10. A method for purifying experimental water based on the apparatus according to any one of claims 1-9, characterized in that, include: S1, Matrix loading: Open the window opening (401) of the outer protective shell (4), load the solid phase extraction matrix (202) onto the stainless steel mesh screen plate (201) of the purification device (2) to ensure uniform distribution of the matrix; tighten the threaded sealing structure of the purification device (2) to ensure the device is airtight. S2, Device connection: Connect the inlet connector (101) of the water inlet (1) tightly to the outlet of the laboratory pure water machine; check the pipe connection between the purification device (2) and the water storage device (3) to confirm that the connection is sealed and there is no leakage; S3, Pure water purification: Press the peristaltic pump start button (402) on the outer protective shell (4), and the peristaltic pump (103) starts; after the flow rate of the water produced by the laboratory pure water machine is stabilized by the water flow stabilizer (102), it is pumped into the purification device (2) at a uniform speed; the pure water is in full contact with the solid phase extraction matrix (202) in the purification device (2), and the perfluorinated and polyfluorinated organic compounds in the water are selectively adsorbed by the matrix; the purified pure water flows into the water storage tank (3) through the outlet connector pipe (205). S4, Pure water storage and use: The ultraviolet lamp (302) on the top of the water storage device (3) is turned on at regular intervals to sterilize the stored pure water and prevent bacterial growth; when the laboratory needs to use the purified pure water, it can be taken directly by opening the outlet (303) of the water storage device (3).

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