Improved Automatic Fluoride Determination Device

Abstract

The present invention discloses an improved automatic fluoride determination device, which includes a frame and a controller. A double-layer sampling mechanism for fluoride sampling, a laser cutting mechanism for shearing filter membranes, a reaction detection mechanism for performing fluoride extraction reaction and detection, and a liquid supply mechanism for providing reaction reagents for the reaction detection mechanism are arranged on the frame; a membrane clip storage and conveying mechanism for storing and sequentially conveying membrane clips to the double-layer sampling mechanism, the laser cutting mechanism, and the reaction detection mechanism is also arranged on the frame; the output end of the controller is respectively connected to the controlled ends of the double-layer sampling mechanism, the laser cutting mechanism, the reaction detection mechanism, and the membrane clip storage and conveying mechanism. By improving the membrane clip storage and conveying mechanism, the sampling mechanism, the cutting mechanism, and the reaction detection mechanism, the present invention improves the detection efficiency and detection accuracy of fluoride.

Description

Technical Field

[0001] The present invention relates to the technical field of fluoride detection, and in particular to an automatic fluoride determination device. Background Art

[0002] There are two types of fluorides in ambient air, gaseous fluorides and particulate fluorides. Gaseous fluorides are mainly hydrogen fluoride, and particulate fluorides mainly include cryolite, fluorite, aluminum fluoride, and phosphorite. The pollution mainly comes from the gases and dusts discharged or escaped from aluminum electrolysis plants, phosphate fertilizer plants, and cryolite plants. When a person is exposed to hydrogen fluoride at a concentration of 400 - 430 mg / m 3 it can cause acute poisoning and death. Long-term inhalation of low-concentration gases and dusts of fluorine and its compounds can affect the normal physiological functions of various tissues and organs, and even cause chronic fluorosis and skeletal fluorosis. Therefore, it is very important to accurately measure the fluorine pollution in ambient air.

[0003] The detection process of fluorides mainly includes three stages: sampling, separation, and analysis of samples. After sampling the fluorides, it is necessary to take out the filter membrane in the membrane clip, separate the fluorides on the filter membrane into a solution, and then analyze and determine the fluorides in the solution.

[0004] Since 2018, the applicant has been researching and developing an automatic fluoride analyzer for measuring the concentration of collected fluorides, and has successively submitted a number of patent applications related to the automatic fluoride analyzer around 2020. One of the prior applications, CN202022958083.9, discloses an automatic fluoride analyzer, which includes a frame and a controller; on the frame, there are successively arranged a membrane clip storage system for storing membrane clips, a sampling device for sampling filter membranes, a shearing device for shearing the sampled filter membranes, and a reaction device located below the shearing device for extracting and determining the fluorides in the sheared filter membranes. On the frame on the other side of the membrane clip storage system, there is a membrane clip automatic pushing device. The controlled ends of the membrane clip automatic pushing device, the sampling device, the shearing device, and the reaction device are respectively connected to the output end of the controller; this device integrates the storage of membrane clips, the pushing of membrane clips, the sampling of filter membranes, the shearing of filter membranes, and the determination of fluorides in filter membranes, and can complete the purpose of measuring fluorides in air through one device, and can continuously measure the fluorides in ambient air without manual supervision.

[0005] However, the following problems were found during the use of the above fluoride automatic analyzer: 1) The storage and transportation of its membrane clip adopt the bottom discharging method. The membrane clip falls by its own gravity into the membrane clip discharging gap between the membrane storage bin and the movable frame body, and then the membrane clip is pushed out from the discharging gap by the push arm driving mechanism; when the membrane clip gets stuck, the equipment cannot work properly, resulting in relatively low efficiency; 2) The ultrasonic oscillator in its reaction device is used to oscillate the solution in the reaction tank. However, due to the special requirements for the oscillation frequency and reaction temperature in the extraction of fluoride on the filter membrane, the oscillation frequency is required to be between 40 and 60 kHz, and the power of the ultrasonic oscillator within this oscillation frequency range is above 30 W. However, due to the small amount of solution in the reaction tank, the solution in the reaction tank is prone to boiling during the operation of the ultrasonic oscillator, resulting in too high a reaction temperature and unable to ensure the detection environment; if the power is reduced, the vibration frequency will not meet the requirements; therefore, it is very difficult to make the solution simultaneously meet the dual requirements of temperature and vibration frequency required for the extraction and reaction of fluoride by directly applying the ultrasonic oscillator to the reaction tank; 3) The liquid storage bag and the reaction tank of its reaction device are of an up-and-down connected structure, and are connected and shut off through a valve in the middle. Since there are a large number of filter membrane fragments in the reaction tank, it is easy for the filter membrane fragments to get stuck between the valve and the inner wall of the reaction tank during the opening and closing of the valve, and liquid leakage will occur during the next use; and a large amount of fragments accumulate in the liquid storage bag for a long time, making the valve unable to open and close normally, affecting the detection accuracy of fluoride. Summary of the Invention

[0006] The technical problem to be solved by the present invention is to provide an improved fluoride automatic determination device to avoid the problem of filter membrane fragment jamming at the liquid discharge place, provide a constant temperature and oscillation frequency for the reaction and extraction of fluoride, and further provide a reliable guarantee for the accuracy of fluoride determination.

[0007] To solve the above technical problems, the following technical solutions are adopted in the present invention.

[0008] The improved fluoride automatic determination device includes a frame and a controller. A double-layer sampling mechanism for fluoride sampling, a laser cutting mechanism for shearing the filter membrane, a reaction detection mechanism for performing fluoride extraction reaction and detection, and a liquid supply mechanism for providing reaction reagents for the reaction detection mechanism are arranged on the frame; a membrane clip storage and transportation mechanism for storing and sequentially transporting the membrane clips to the double-layer sampling mechanism, the laser cutting mechanism, and the reaction detection mechanism is also arranged on the frame; the output end of the controller is respectively connected to the controlled ends of the double-layer sampling mechanism, the laser cutting mechanism, the reaction detection mechanism, and the membrane clip storage and transportation mechanism.

[0009] The above-mentioned improved fluoride automatic determination device, wherein the membrane clip storage and conveying mechanism includes a membrane storage bin vertically installed on the frame. One end face of the membrane storage bin is open. An elevating module is arranged on the frame behind the membrane storage bin for lifting the membrane clips stored in the membrane storage bin to the discharge port. An unloading tray for carrying a single membrane clip is arranged on the frame on one side of the top of the membrane storage bin. A horizontal translation module is arranged on the frame above the unloading tray for horizontally pulling the membrane clip from the discharge port of the membrane storage bin to the unloading tray. A longitudinal translation module is arranged on the frame behind the unloading tray for pushing the membrane clip on the unloading tray to the sampling mechanism. The controlled ends of the elevating module, the horizontal translation module and the longitudinal translation module are respectively connected to the output end of the controller.

[0010] The above-mentioned improved fluoride automatic determination device, wherein the elevating module includes an elevating bracket fixedly arranged on the frame. An elevating drive motor is fixedly arranged at the top of the elevating bracket. An elevating lead screw is installed between the upper and lower end plates of the elevating bracket through bearings. The top end of the elevating lead screw is connected to the output shaft of the elevating drive motor. An elevating block is threadedly connected to the elevating lead screw. A membrane clip support plate connected to the elevating block and capable of rising and falling in the membrane storage bin is horizontally arranged in the membrane storage bin.

[0011] The above-mentioned improved fluoride automatic determination device, wherein two membrane storage bins are symmetrically arranged on the left and right of the frame. One set of elevating modules is respectively arranged corresponding to the two membrane storage bins. The horizontal translation module is located above the space between the two membrane storage bins. The unloading tray is located between the discharge ports of the two membrane storage bins. The longitudinal translation module is located behind the unloading tray between the two membrane storage bins.

[0012] The above-mentioned improved fluoride automatic determination device, wherein the double-layer sampling mechanism includes a top sealing component and a mounting plate arranged in parallel up and down. The mounting plate is fixedly arranged on the frame. The top sealing component and the mounting plate are fixedly connected by four linear optical axes fixedly arranged at the corners. A vertical sampling tube is communicated at the center of the top sealing component. A bottom sealing component sleeved on the linear optical axis is also arranged between the top sealing component and the mounting plate. A membrane clip component for clamping the membrane clip is arranged between the top sealing component and the bottom sealing component. The membrane clip component is a double-layer membrane clip arranged side by side up and down. A drive motor is fixedly arranged on the mounting plate. The output end of the drive motor is connected to a drive component for driving the bottom sealing component to move up and down to realize the opening and closing of the membrane clip component. A through hole is opened at the center of the mounting plate. An air extraction pipe coaxial with the sampling tube is arranged in the through hole. The top end of the air extraction pipe is communicated with the center of the bottom sealing component. The bottom end of the air extraction pipe is connected to a blower through a hose.

[0013] The above-mentioned improved fluoride automatic measuring device, the membrane clamp assembly includes an upper membrane clamp tray and a lower membrane clamp tray arranged in parallel up and down, the lower membrane clamp tray is arranged on the top end surface of the bottom sealing assembly through four second springs, the top end surface of the lower membrane clamp tray is fixedly provided with an intermediate sealing assembly, and the upper membrane clamp tray is arranged on the top end surface of the intermediate sealing assembly through four second springs; the centers of the top sealing assembly, the intermediate sealing assembly and the bottom sealing assembly are all provided with through holes corresponding to the size of the air flow holes on the membrane clamp for the sampled gas to flow from the sampling tube to the exhaust tube.

[0014] The above-mentioned improved fluoride automatic determination device, the reaction detection mechanism includes a standard liquid component, a reaction component, a determination component and a controller arranged on a frame, the frame is also provided with a reaction moving component for controlling the horizontal movement of the reaction component, a water tank component for providing a circulating medium for the reaction component and recovering reaction waste liquid is arranged between the reaction component and the reaction moving component, the reaction component adopts a plunger-type side discharge method to discharge waste liquid into the water tank component; the output end of the controller is respectively connected to the controlled end of the standard liquid component, the reaction component, the determination component, the reaction moving component and the water tank component.

[0015] The above-mentioned improved fluoride automatic measuring device, the reaction moving assembly includes a horizontal mounting frame fixedly mounted on the frame laterally, a horizontal driving motor is fixedly arranged on one side of the horizontal mounting frame, the output end shaft of the horizontal driving motor is connected to a screw rod lying horizontally in the horizontal mounting frame and located below the reaction assembly, and a moving block matched with the screw rod thread is also slidably arranged in the horizontal mounting frame; the water tank assembly is fixedly arranged on the moving block.

[0016] The above-mentioned improved fluoride automatic measuring device, the water tank assembly includes a water tank fixedly mounted on the moving block, the top of the water tank is open; a circulating water pump connected to the inner cavity of the water tank and used to transport the circulating medium to the reaction assembly is fixedly mounted on the outer wall of one side of the water tank, and a drainage pump is arranged on the outer wall of the other side of the water tank; a stainless steel filter is mounted on the top of the water tank.

[0017] In the above-mentioned improved fluoride automatic determination device, a vertical mounting frame is further fixedly arranged on the moving block. The back of the vertical mounting frame is fixedly connected to the water tank. On the top surface of the vertical mounting frame, a reactor is fixedly arranged and communicated with the water tank for receiving the circulating medium conveyed by the water tank. The reactor is a cuboid structure with a cavity inside. An ultrasonic vibrator for providing a vibration frequency for the circulating medium in the reactor is installed on the outer wall of the reactor. Horizontally arranged side by side in the reactor are a vertical first reaction cup and a second reaction cup that are not communicated with the inner cavity of the reactor. Waste liquid pipes are respectively arranged on the lower side walls of the first reaction cup and the second reaction cup extending out of the bottom of the reactor and facing the stainless steel filter screen at the top of the side water tank. A plunger type switch mechanism is arranged on the vertical mounting frame and extends vertically upward, and the top thereof extends into the lower parts of the first reaction cup and the second reaction cup to control the opening and closing of the waste liquid pipes.

[0018] Due to the adoption of the above technical solutions, the technical progress achieved by the present invention is as follows.

[0019] The membrane clip storage and conveying mechanism of the present invention uses a lifting method for discharging materials, which can push the membrane clip out of the membrane storage bin smoothly. Combined with the monitoring of the photoelectric sensor, it can accurately control the cooperation of the horizontal lateral translation module and the vertical translation module to push the membrane clip to the sampling mechanism, overcoming the problem that the membrane clip is prone to jamming when relying on gravity for discharging, thus reliably ensuring that the fluoride automatic determination device can continuously and stably perform detection and improving the work efficiency.

[0020] The sampling mechanism adopts a double-layer method, and combined with the sampling tube and the exhaust pipe adopting a vertically through sampling and air inlet method, the fluoride in the sampling gas can be quickly attached to the upper and lower layers of filter membranes, greatly improving the accuracy of fluoride sampling.

[0021] The reaction detection mechanism adopts a plunger type side drainage structure, avoiding the problem of filter membrane fragment jamming at the drainage place. Moreover, the water tank is provided with an open top, which is convenient for the collection and cleaning of filter membrane fragments in the waste liquid. The present invention realizes the purpose of providing a constant temperature and a constant vibration frequency for the solution in the reactor by setting a circulating medium and a reactor, and at the same time placing the reaction cup in the circulating medium of the reactor. When an ultrasonic vibrator provides a vibration frequency, the solution in the reaction cup is cooled through the circulating medium, effectively preventing the problem that the solution in the cup boils due to the direct action of the high-power ultrasonic vibrator on the reaction cup, and further providing a reliable guarantee for the accuracy of fluoride determination. Description of the Drawings

[0022] Figure 1 Structural schematic of the present invention Figure 1 ;

[0023] Figure 2 Structural schematic of the present invention Figure 2 ;

[0024] Figure 3 It is a schematic structural diagram of the membrane clip storage and conveying mechanism of the present invention;

[0025] Figure 4 It is an exploded view of the double-layer sampling mechanism of the present invention;

[0026] Figure 5 It is a schematic structural diagram of the membrane clip assembly of the present invention;

[0027] Figure 6 It is a schematic structural diagram of the reaction detection mechanism of the present invention;

[0028] Figure 7 It is a schematic structure of the membrane clip of the present invention Figure 1 ;

[0029] Figure 8 It is a schematic structure of the membrane clip of the present invention Figure 2 .

[0030] Wherein:

[0031] 1. Frame,

[0032] 2. Controller,

[0033] 3. Membrane clip storage and conveying mechanism, 31. Membrane storage bin, 311. Slide groove, 32. Lifting module, 321. Lifting bracket, 322. Lifting lead screw, 323. Lifting drive motor, 324. Lifting block, 325. Membrane clip support plate, 326. Discharge port, 327. Photoelectric sensor, 33. Horizontal translation module, 331. Horizontal push plate, 34. Longitudinal translation module, 341. Longitudinal push plate, 35. Discharge tray;

[0034] 4. Double-layer sampling mechanism, 41. Sampling tube, 42. Top sealing assembly, 421. Top lower pressing block, 43. Mounting plate, 44. Bottom sealing assembly, 441. Bottom upper pressing block, 442. Bottom gas collecting block, 45. Exhaust duct, 46. Fan, 47. Drive motor, 48. Lead screw, 49. Pressing assembly, 410. First spring, 411. Lower membrane clip tray, 412. Upper membrane clip tray, 413. Second spring, 414. Linear optical axis, 415. Membrane clip, 416. Sealing ring, 417. Indicator rod, 418. Photoelectric sensor, 419. Flowmeter, 420. Intermediate sealing assembly, 4201. Middle upper pressing block;

[0035] 5. Laser cutting mechanism,

[0036] 6. Liquid supply mechanism,

[0037] 7. Reaction detection mechanism, 711. Standard liquid cup, 712. Inverted U-shaped bracket, 721. Horizontal mounting frame, 722. Horizontal drive motor, 731. Reactor, 7311. Liquid inlet pipe, 7312. Overflow pipe, 732. Liquid injection head, 734. Second reaction cup, 735. Waste liquid pipe, 739. Ultrasonic vibrator; 741. Lifting module, 742. Electrode, 743. Sensor, 744. Electrode protection cup; 75. Water tank, 751. Water inlet, 752. Stainless steel filter, 753. Circulating water pump, 754. Discharge pump, 755. Liquid level sensor.

[0038] 81. Upper cover, 811. Annular groove, 812. Upper cover through hole, 82. Lower cover, 821. Annular protrusion, 822. Lower cover through hole, 83. Filter membrane. DETAILED DESCRIPTION

[0039] The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.

[0040] An improved automatic fluoride determination device, such as Figures 1 to 2 As shown, it includes a frame 1, a controller 2, a membrane clamp storage and conveying mechanism 3, a double-layer sampling mechanism 4, a laser cutting mechanism 5, a reaction detection mechanism 7, a liquid supply mechanism 6 and a waste membrane clamp collection bin. The output end of the controller is respectively connected to the controlled ends of the double-layer sampling mechanism, the laser cutting mechanism 5, the reaction detection mechanism 7 and the membrane clamp storage and conveying mechanism 3, so as to control the coordinated operation of each mechanism to complete the operations such as membrane clamp transportation, fluoride sample collection, filter membrane shearing, fluoride extraction and detection.

[0041] The membrane clamp storage and conveying mechanism 3 is used to store the membrane clamps, and convey the membrane clamps to the double-layer sampling mechanism, the laser cutting mechanism 5, the reaction detection mechanism 7 and the waste membrane clamp collection bin in sequence under the instruction of the controller.

[0042] The membrane clamp is a medium for sampling, and its sealing performance is very important for the accuracy of fluoride detection. In order to ensure the sealing performance of the membrane clamp, the present invention improves the structure of the membrane clamp. The specific structure is as follows Figure 7 and Figure 8 As shown, it includes an upper cover 81 and a lower cover 82, wherein the upper cover is embedded and clamped in the lower cover 82; and the filter membrane 83 is located between the upper cover and the lower cover.

[0043] In this embodiment, both the upper cover and the lower cover are square structures, an upper cover through hole 812 is provided at the center of the upper cover 81, and a lower cover through hole 822 is provided at the center of the lower cover 82. Both the upper cover through hole and the lower cover through hole are circular holes. The upper cover through hole and the lower cover through hole are provided for the determination device to sample and shear the filter membrane 83 attached with fluoride.

[0044] To improve the sealing performance after the upper cover and the lower cover clamp the filter membrane, the present invention provides an annular groove 811 on the bottom end surface of the upper cover 81 near the through hole of the upper cover, as Figure 7 shown; an annular protrusion 821 is provided on the upper end surface of the lower cover corresponding to the annular groove, as Figure 8 shown; the annular protrusion and the annular groove are fitted together to compress the filter membrane. In this embodiment, both the annular groove and the annular protrusion are circular rings.

[0045] A positioning groove is provided on the top end surface of the lower cover, and the positioning groove is used to position the filter membrane and the upper cover. A number of limiting edges pointing to the inside of the positioning groove are provided at the junction of the top end surface of the lower cover and the inner side wall of the positioning groove. Each limiting edge and the inner side wall of the positioning groove form an upper cover positioning groove. A number of flanges adapted to the upper cover positioning groove are provided on the side wall of the upper cover. The bottom end surface of the limiting edge is in close contact with the top end surface of the flange, and is used to clamp the upper cover in the lower cover.

[0046] When using this membrane clamp to clamp the filter membrane, directly place the filter membrane on the lower cover, then buckle the upper cover above the filter membrane. By pressing down and making the annular protrusion of the lower cover fit into the annular groove of the upper cover, and at the same time the upper cover is fitted into the positioning groove of the lower cover, the limiting edge of the lower cover clamps the edge of the upper cover; the clamping work can be completed. Its clamping operation of the filter membrane is realized through the clamping structure of the annular groove and the annular protrusion, which ensures the airtightness between the filter membrane and the membrane clamp, and further ensures the subsequent sampling accuracy.

[0047] The structure of the membrane clamp storage and conveying mechanism 3 is as Figure 3 shown, including a film storage bin 31, a lifting module 32, a horizontal translation module 33, a vertical translation module 34 and a discharging tray 35. The controlled ends of the lifting module 32, the horizontal translation module 33 and the vertical translation module 34 are respectively connected to the output end of the controller, and coordinate actions under the command of the controller.

[0048] In order to facilitate the storage of fluoride sampling membrane clamps of different properties, in this embodiment, two sets of film storage bins 31 and lifting modules 32 are provided. The two sets of film storage bins 31 share a set of horizontal translation module 33, vertical translation module 34 and discharging tray 35, and its structure is as Figure 3 shown; specifically: two film storage bins are symmetrically arranged on the left and right on the rack. A set of lifting modules 32 are respectively provided corresponding to the two film storage bins. The horizontal translation module 33 is located above the two film storage bins. The discharging tray 35 is located between the discharging ports 326 of the two film storage bins. The vertical translation module 34 is located behind the discharging tray 35 between the two film storage bins.

[0049] The film storage bin 31 is vertically installed on the frame and is used to store film clips; the top of the film storage bin is the discharge port for transporting single film clips outwards. To facilitate placing film clips into the film storage bin, one side end face of the film storage bin 31 can be set to be open. After the film clips are placed, side plates are used to seal the film storage bin.

[0050] The discharge tray 35 is used to carry single film clips taken out from the left film storage bin or the right film storage bin, and its top end face is flush with the top end face of the discharge port of the film storage bin.

[0051] The lifting module 32 is paired and installed with the film storage bin 31. In the present invention, the lifting module 32 is arranged on the frame behind the film storage bin 31 and is used to lift the film clips stored in the film storage bin to the discharge port at the top of the film storage bin.

[0052] The lifting module 32 includes a lifting bracket 321 fixedly arranged on the frame. At the top of the lifting bracket 321, a lifting drive motor 323 is fixedly arranged. Between the upper and lower end plates of the lifting bracket 321, a lifting lead screw 322 is installed through bearings. The top end of the lifting lead screw 322 is connected to the output shaft of the lifting drive motor; a lifting block 324 is threadedly connected to the lifting lead screw.

[0053] A film clip support plate 325 is horizontally arranged in the film storage bin for supporting and placing film clips; a through hole is longitudinally opened on the rear end face of the film storage bin, and the through hole corresponds to the up and down walking path of the lifting block; the film clip support plate 325 is fixedly connected to the lifting block through a connecting rod, and the connecting rod is inserted through the through hole. The film clip support plate 325 can be lifted and lowered in the film storage bin driven by the lifting block, thereby driving the film clips thereon to move up or down.

[0054] In the present invention, in order to accurately sense whether the film clip reaches the discharge port, a photoelectric sensor is arranged at the discharge port of the film storage bin. The output end of the photoelectric sensor is connected to the input end of the controller and is used to send the signal of detecting the film clip to the controller, so that the controller controls the lifting module 32, the horizontal translation module 33 and the vertical translation module 34 to coordinate and operate to complete the taking out and pushing of the film clip.

[0055] When all the film clips in the film storage bin are taken out, the lifting module will drive the film clip support plate to descend to the bottom of the film storage bin. To prevent the lifting module from descending beyond the limit, a photoelectric sensor 327 is also arranged at the lower end plate of the lifting bracket, as Figure 3 shown, and is used to detect whether the lifting block descends to the lowest position.

[0056] The horizontal translation module 33 is arranged on the frame above the discharge tray, straddling two film storage bins, and is used to horizontally pull the film clip from the discharge port of the film storage bin to the discharge tray 35.

[0057] The horizontal translation module 33 includes a horizontal transverse bracket. A horizontal transverse driving motor is fixedly arranged at one end of the transverse bracket. A horizontal transverse lead screw is installed between the left and right end plates of the transverse bracket through bearings. One end of the horizontal transverse lead screw is connected to the output shaft of the horizontal transverse driving motor; a transverse moving block is threadedly connected to the horizontal transverse lead screw, and a transverse pushing plate 331 is arranged below the transverse moving block. Hanging edges are respectively arranged at the left and right side edges of the bottom end face of the transverse pushing plate 331 for hooking a single film clip at the discharging port of the film storage bin.

[0058] The longitudinal translation module 34 is located on the frame behind the discharging tray 35 and is used to push the single film clip on the discharging tray 35 into the sampling mechanism. After sampling, the film clip is continuously pushed into the shearing mechanism, and after shearing, it is pushed into the waste film bin.

[0059] The longitudinal translation module 34 includes a horizontal longitudinal bracket. A longitudinal translation driving motor is fixedly arranged at one end of the longitudinal bracket. A horizontal longitudinal lead screw is installed between the front and rear end plates of the longitudinal bracket through bearings. One end of the horizontal longitudinal lead screw is connected to the output shaft of the longitudinal translation driving motor; a longitudinal moving block is threadedly connected to the horizontal longitudinal lead screw, and a longitudinal pushing plate 341 is arranged above the longitudinal moving block. The longitudinal pushing plate 341 moves back and forth above the discharging tray 35 to push the single film clip on the discharging tray into the sampling mechanism. After sampling, the film clip is continuously pushed into the shearing mechanism, and after shearing, it is pushed into the waste film bin.

[0060] When the membrane clip storage and conveying mechanism is used to store membrane clips, first, the controller controls the lifting module 32 to move the lifting block to the lowest position. At this time, the membrane clip support plate 325 is also at the bottom of the membrane storage bin. The photoelectric sensor at the bottom detects that the lifting block is in place and sends a signal to the controller, and the controller controls the lifting module 32 to stop working. Subsequently, the sorted membrane clips can be placed on the membrane clip support plate 325 from the side opening of the membrane storage bin. Secondly, the controller controls the lifting module 32 to lift the lifting block. As the lifting block moves upward, the topmost membrane clip on the membrane clip support plate reaches the discharge port 326 of the membrane storage bin first. At this time, after the photoelectric sensor at the discharge port detects the membrane clip, it sends a signal to the controller. The controller controls the lifting module to stop moving, and at the same time controls the horizontal translation module 33 to move, moving the horizontal pushing plate to the discharge port. When the photoelectric sensor at the discharge port detects the arrival of the horizontal pushing plate, it sends a signal to the controller. The controller controls the horizontal translation module to stop moving, and at the same time controls the lifting module to continue moving upward by a distance equal to the thickness of a membrane clip, so that the topmost membrane clip tightly adheres to the bottom end surface of the horizontal pushing plate, and the hanging edge hook of the horizontal pushing plate hooks the outer edge of the membrane clip. After that, the controller reversely drives the horizontal translation module 33, and the horizontal translation module drives the horizontal pushing plate to pull out the hooked membrane clip and place it on the discharge tray 35. Then, the controller controls the longitudinal translation module 34 to move, and the single membrane clip on the discharge tray is pushed longitudinally by the longitudinal pushing plate 341 into the sampling mechanism for sampling. Subsequently, the longitudinal translation module 34 is controlled to reset; that is, the conveying operation of a single membrane clip is completed.

[0061] The double-layer sampling mechanism 4 is used for the sampling of fluorides, and its structure is as Figure 4 shown, including a top sealing component 42, a membrane clip component, a bottom sealing component 44, a driving component, and a mounting plate 43 arranged in sequence from top to bottom. Among them, the top sealing component 42 and the mounting plate 43 are arranged parallel up and down, and the mounting plate 43 is fixedly arranged on the frame.

[0062] The top sealing component 42 and the mounting plate 43 are fixedly connected by four linear optical axes 414 fixedly arranged at the corners. The bottom sealing component 44 is located between the top sealing component 42 and the mounting plate 43 and is sleeved on the linear optical axes 414, and the membrane clip component is located above the bottom sealing component 44.

[0063] A driving motor 47 is fixedly arranged on the mounting plate. The output end of the driving motor 47 is connected to the driving component, which is used to drive the bottom sealing component to move up and down to realize the opening and closing of the membrane clip component.

[0064] The sampling tube 41 is vertically communicated at the center of the top sealing component 42. A through hole is opened at the center of the mounting plate 43, and an exhaust duct 45 is inserted through the through hole. The exhaust duct 45 is coaxially arranged with the sampling tube. The top end of the exhaust duct 45 is centrally communicated with the bottom sealing component 44, and the bottom end of the exhaust duct 45 is connected to a fan 46 through a hose, forming an up-and-down through air duct.

[0065] In this embodiment, the membrane clip assembly is a double-layer membrane clip arranged side by side up and down; its structure is as shown in Figure 4 and Figure 5 shown, including an upper membrane clip tray 412 and a lower membrane clip tray 411 arranged side by side up and down. The lower membrane clip tray 411 is arranged on the top surface of the bottom sealing assembly 44 through four second springs 413. An intermediate sealing assembly 420 is fixedly arranged on the top surface of the lower membrane clip tray 411. The upper membrane clip tray 412 is arranged on the top surface of the intermediate sealing assembly 420 through four second springs 413. Through holes are opened in the centers of the top sealing assembly 42, the intermediate sealing assembly 420, and the bottom sealing assembly 44, and the sizes of the through holes correspond to the air flow holes on the membrane clip, so that the sampling gas flows from the sampling pipe 41 to the exhaust pipe 45.

[0066] To improve the sealing performance during sampling, the present invention provides a top-down pressing block 421 on the bottom surface of the top sealing assembly 42, and a middle-upper pressing block 4201 on the top surface of the intermediate sealing assembly 420. When pressing the upper membrane clip, the top-down pressing block 421 will extend into the upper membrane clip tray 412, and the middle-upper pressing block 4201 will also extend into the upper membrane clip tray 412. The top-down pressing block 421 and the middle-upper pressing block 4201 clamp and press the upper membrane clip up and down. At the same time, a bottom-upper pressing block 441 is provided on the top surface of the bottom sealing assembly 44. When pressing the lower membrane clip, the bottom-upper pressing block 441 extends into the lower membrane clip tray 411 and presses the lower membrane clip against the bottom surface of the intermediate sealing assembly 420. To further improve the sealing performance, in this embodiment, sealing rings 416 are provided on the top surfaces of the middle-upper pressing block 4201 and the bottom-upper pressing block 441. When pressing the membrane clip, they wrap around the edge of the membrane clip, effectively preventing the escape of the sampling gas.

[0067] The driving assembly is used to drive the bottom sealing assembly 44 to move up and down under the action of the driving motor, so as to realize the opening and closing of the membrane clip assembly. When the membrane clip assembly is closed, the sampling operation can be carried out; when the membrane clip assembly is opened, the membrane clip can be replaced.

[0068] The driving assembly includes a lead screw 48, a pressing assembly 49, and a first spring 410. Among them, the pressing assembly 49 is located between the bottom sealing assembly 44 and the mounting plate 43 and is slidably arranged on the linear optical axis 414. The driving motor 47 is fixedly arranged on the bottom surface of the mounting plate. The bottom end of the lead screw 48 passes through the mounting plate and is axially connected to the output end of the driving motor; the top end of the lead screw 48 passes through the pressing assembly and is threadedly connected to the pressing assembly; the first spring 410 is sleeved on the linear optical axis between the pressing assembly 49 and the bottom sealing assembly 44.

[0069] To improve flexibility, the present invention provides two pressing assemblies 49, and each pressing assembly is sleeved on two linear optical axes on the same side, as shown in Figure 4As shown in the figure; correspondingly, the number of driving motors and lead screws is also two sets respectively, which drive two pressing components respectively.

[0070] During the process of the driving motor pressing the membrane clip upward, in order to prevent excessive tightening, the present invention also fixedly arranges an indicating rod 417 on the top surface of the pressing component. The indicating rod is vertically upward, sequentially passes through the bottom sealing component 44 and the top sealing component 42. An upper and lower limit label is arranged at the top of the indicating rod above the top sealing component. A photoelectric sensor 418 is arranged on the top surface of the top sealing component for capturing the limit label; the output end of the limit sensor is connected to the input end of the controller, and the output end of the controller is connected to the controlled end of the driving motor.

[0071] The setting position of the limit label coincides with the up and down stroke of the pressing component. When the membrane clip is clamped, the lower limit label is just captured by the photoelectric sensor, and the photoelectric sensor sends this signal to the controller, and the controller then controls the driving motor to stop operating. When the membrane clip is opened, the upper limit label is just captured by the photoelectric sensor, and the photoelectric sensor sends this signal to the controller, and the controller then controls the driving motor to stop operating.

[0072] In the present invention, a flow meter 419 is also installed in the exhaust pipe 45 through a three-way valve for measuring the amount of sampled gas flowing through.

[0073] When the present invention is used for sampling fluoride, the controller controls the driving motor to act, and the pressing component moves upward. Through the cooperation of the bottom sealing component and the top sealing component, the membrane clip component is pressed tightly, and a sealed air flow channel is formed between the sampling pipe and the exhaust pipe; the controller starts the fan, and the sampled gas passes through the upper membrane clip, the lower membrane clip and the exhaust pipe in sequence from the sampling pipe and then is discharged from the fan; the fluoride in the sampled gas adheres to the filter membrane in the membrane clip. Through two times of filtering up and down, all the fluoride in the sampled gas can be collected, improving the sampling accuracy.

[0074] When the membrane clip needs to be replaced, the controller controls the driving motor to act in the reverse direction, and the pressing component moves downward. The bottom sealing component, the lower membrane clip tray, the upper membrane clip tray and the top sealing component are separated in sequence, and the membrane clip is exposed; the controller controls the longitudinal translation module 34 to push the membrane clip from the upper membrane clip tray and the lower membrane clip tray to the shearing mechanism, and the lifting module 32 and the transverse translation module 33 cooperate to replace the membrane clip.

[0075] The laser cutting mechanism 5 is used to cut the filter membrane with fluoride attached in the membrane clip, so that the cut filter membrane fragments fall into the reaction detection mechanism, which is convenient for the extraction of fluoride. The laser cutting mechanism 5 mainly includes a laser head and a laser moving module. The laser moving module realizes the horizontal transverse and longitudinal movement, drives the laser head to move under the instruction of the controller, and the laser head generates a cutting effect on the filter membrane in the filter membrane clip, dividing it into fragments. The divided filter membrane fragments directly fall into the reaction detection mechanism.

[0076] The reaction detection mechanism 7 is used for the extraction, reaction and detection of fluoride. In the present invention, the reaction detection mechanism adopts a plunger structure, and its structure is as Figure 6 shown, including a standard solution assembly, a reaction moving assembly, a reaction assembly, a determination assembly and a water tank assembly arranged on the frame. The output end of the controller is respectively connected to the controlled ends of the above-mentioned components to control the coordinated operation of each component and complete the extraction and reaction operations of fluoride.

[0077] In the present invention, the reaction moving assembly is used to control the horizontal movement of the reaction assembly, so that the two reaction cups in the reaction assembly sequentially complete reagent filling, filter membrane fragment receiving and electrode detection.

[0078] The reaction moving assembly includes a horizontal mounting frame 721, a horizontal driving motor 722, a lead screw, a moving block and a vertical fixing frame. The horizontal mounting frame 721 is horizontally and fixedly mounted on the frame. The horizontal driving motor 722 is fixedly arranged on one side of the horizontal mounting frame, and the controlled end of the horizontal driving motor 722 is connected to the output end of the controller; the lead screw lies horizontally in the horizontal mounting frame and is located below the reaction assembly. One end of the lead screw is axially connected to the output end of the horizontal driving motor, and the other end of the lead screw is connected to the horizontal mounting frame 721 through a bearing; the moving block is slidably arranged in the horizontal mounting frame 721 and is threadedly fitted with the lead screw, and moves left and right on the lead screw under the action of the horizontal driving motor.

[0079] Both the water tank assembly and the vertical fixing frame are fixedly arranged on the moving block, and the back of the vertical mounting frame is fixedly connected to the water tank 75.

[0080] The water tank assembly is used to provide a circulating medium for the reaction assembly and recycle the reaction waste liquid; the reaction assembly discharges the waste liquid into the water tank assembly in a plunger side liquid discharge manner.

[0081] In the present invention, the water tank assembly includes a water tank 75 fixedly arranged on the moving block. The top of the water tank is open, and a stainless steel filter screen 752 is erected on the top of the water tank to filter the filter membrane fragments in the waste liquid discharged from the reaction assembly for timely cleaning; the side without the stainless steel filter screen is the water filling port 751 of the water tank, which is convenient for filling the circulating medium into the water tank, such as Figure 6 shown. In this embodiment, the circulating medium is water.

[0082] A circulating water pump 753 is fixedly arranged on the outer wall of one side of the water tank. The liquid inlet of the circulating water pump 753 is communicated with the inner cavity of the water tank through a pipeline, and the liquid outlet of the circulating water pump 753 is communicated with the reaction assembly through a pipeline. The controlled end of the circulating water pump 753 is connected to the output end of the controller and is used to transport the circulating medium to the reaction assembly under the instruction of the controller. The setting of the circulating medium can ensure the reaction temperature and vibration frequency required by the reaction assembly. In this embodiment, a liquid level sensor 755 is also arranged on the side wall of the water tank, such asFigure 6 As shown, it is used to detect the liquid level of the circulating medium in the water tank.

[0083] The top of the water tank provided with a stainless steel filter screen is vertically opposite to the liquid outlet of the reaction assembly, and is used to collect the waste liquid discharged after the reaction and the circulating medium overflowing from the reaction assembly. At the bottom of the outer wall on the other side of the water tank, a liquid discharge pump 754 is provided. The liquid discharge pump 754 is communicated with the inner cavity of the water tank, and the controlled end of the liquid discharge pump is connected to the output end of the controller, and is used to discharge the waste liquid from the water tank under the instruction of the controller to keep the amount of the circulating medium in the water tank constant.

[0084] The reaction assembly includes a reactor 731, a liquid injection head 732, a plunger-type switching mechanism, an ultrasonic oscillator 739 and a stirring mechanism.

[0085] The reactor 731 is fixedly arranged on the top surface of the vertical mounting frame and is a cuboid structure with a cavity inside. The inner cavity of the reactor 731 is communicated with the water tank and is used to receive the circulating medium conveyed by the water tank.

[0086] At the bottom of the reactor 731, a liquid inlet pipe 7311 for inputting the circulating medium into the inner cavity is provided, and the liquid inlet pipe 7311 is communicated with the pipeline connected to the liquid outlet of the circulating water pump 753; at the top of the reactor 731, an overflow pipe 7312 for overflowing the circulating medium is provided, and the overflow pipe 7312 is a bent pipe with an outlet facing the top of the water tank, as Figure 6 shown.

[0087] In the reactor 731, a vertical first reaction cup and a second reaction cup 734 are horizontally arranged in parallel, as Figure 6 shown; the first reaction cup and the second reaction cup 734 are not communicated with the inner cavity of the reactor, that is, the circulating medium in the reactor and the reaction solution in the inner cavity of the reaction cup will not be mixed during the reaction process; in the present invention, the tops of the first reaction cup and the second reaction cup 734 extend upward out of the reactor 731 to facilitate docking with the liquid injection head and the electrodes of the measuring assembly; the bottoms of the first reaction cup and the second reaction cup 734 extend downward out of the reactor 731.

[0088] On the lower side walls of the first reaction cup and the second reaction cup 734 extending out of the bottom of the reactor, waste liquid pipes 735 are respectively provided; the waste liquid pipes are arranged obliquely downward, and the liquid outlet faces the stainless steel filter screen of the side water tank.

[0089] The plunger-type switching mechanism is vertically arranged upward on the vertical mounting frame, and the top of the plunger-type switching mechanism extends into the lower parts of the first reaction cup and the second reaction cup 734 and is used to control the opening and closing of the waste liquid pipe.

[0090] In the present invention, the structure of the switching mechanism includes a lifting motor fixedly arranged in a vertical mounting frame, and the controlled end of the lifting motor is connected to the output end of the controller; the output shaft of the lifting motor is connected to a plug body inserted into the reaction cup, and a plug cover is assembled on the top end of the plug body. Sealing rings are respectively embedded on the circumferential walls of the plug body and the plug cover to prevent the reaction solution in the inner cavity of the reaction cup from leaking.

[0091] When the reaction cup is performing a reaction operation, under the command of the controller, the lifting motor controls the plug body and the plug cover to move upward to seal the waste liquid pipe 735; when the reaction operation is completed, under the command of the controller, the lifting motor controls the plug body and the plug cover to move downward, so that the inner cavity of the reaction cup is communicated with the waste liquid pipe, and the reaction solution and filter membrane fragments in the reaction cup can flow to the water tank through the waste liquid pipe.

[0092] In the present invention, a stirring mechanism is arranged on the switching mechanism and is used for stirring the reaction solution in the reaction cup during the reaction process. The structure of the stirring mechanism includes a stirring motor and a stirring impeller. The stirring motor is fixedly arranged in the plug body, and the controlled end of the stirring motor is connected to the output end of the controller; the stirring impeller is located in the inner cavity of the reaction cup, the rotating shaft of the stirring impeller is assembled with the plug cover through a sealing bearing, and the output shaft of the stirring motor passes through the top end of the plug body and is connected to the rotating shaft of the stirring impeller through a coupling.

[0093] The ultrasonic oscillator 739 is installed on the outer side wall of the reactor and is used to provide a vibration frequency. When the ultrasonic oscillator works, ultrasonic waves will be transmitted into the circulating medium and then transmitted to the solution in the reaction cup to provide the vibration frequency required for fluoride extraction. During this process, the heat generated by the ultrasonic waves will heat the circulating medium, and the controller can start the circulating water pump according to the detected temperature value of the circulating medium to accelerate the flow of the circulating medium and cool the circulating medium in the reactor, further reducing the temperature of the solution in the reaction cup, and reliably ensuring the temperature required for the reaction.

[0094] The liquid injection head 732 is fixedly arranged on the frame of the measuring device and is used to inject the reagents required for the reaction into the first reaction cup and the second reaction cup respectively under the command of the controller when the reactor moves left and right.

[0095] To accurately control the moving position of the reactor and facilitate the positioning of the first reaction cup and the second reaction cup, in this embodiment, photoelectric sensors are arranged on the side wall of the horizontal mounting frame 721, and the positions of the two photoelectric sensors respectively correspond to the first reaction cup and the second reaction cup. The output ends of the photoelectric sensors are both connected to the input end of the controller; the controller monitors the position of the moving block through the photoelectric sensors to judge the positions of the first reaction cup and the second reaction cup.

[0096] The structure of the standard solution assembly is as Figure 6As shown in the figure, it includes an inverted U-shaped bracket 712 fixedly arranged on the frame. A standard solution cup 711 for containing the standard solution is fixedly arranged at the top of the inverted U-shaped bracket 712. The inverted U-shaped bracket 712 also facilitates providing a walking space for the drainage pump when the water tank assembly moves left and right.

[0097] The structure of the measurement assembly is as Figure 6 shown in the figure, and it includes a lifting module 741 fixedly arranged on the frame. The controlled end of the lifting module is connected to the output end of the controller, and the moving end of the lifting module is connected with an electrode 742. An electrode protection cup 744 is also fixedly arranged on the vertical mounting frame. The electrode protection cup 744 is arranged in parallel with the reactor 731 and is used to place the electrode when fluoride detection is not carried out, thereby protecting the electrode. In this embodiment, a sensor 743 is also arranged at the bottom end of the lifting module 741. The output end of the sensor is connected to the input end of the controller. The sensor is used to sense whether the electrode protection cup is exactly below the electrode, so that the lifting module can accurately lower the electrode into the electrode protection cup.

[0098] The liquid supply mechanism 6 is used to provide reaction reagents for the reaction detection mechanism, including a standard solution storage tank, a buffer solution storage tank, a hydrochloric acid storage tank, a sodium hydroxide storage tank, etc.; each storage tank is added to the reaction cup through a corresponding liquid addition pump.

[0099] The waste membrane clip collection bin is arranged on the frame on one side of the laser cutting mechanism and is used to collect the waste membrane clips after shearing. The membrane clip storage and conveying mechanism can push the waste membrane clips after being sheared by the laser cutting mechanism into the waste membrane clip collection bin.

[0100] When the present invention is used to measure fluoride in ambient air, its specific working process is as follows.

[0101] S1. Prepare the standard solution and draw the standard curve.

[0102] The concentrated solution in the standard solution storage tank is filled into the standard solution cup to prepare the standard solution for standby; in the early stage of the test, the controller controls the liquid injection head to add the standard solution into the reaction cup, and measures the voltage values of fluorides with different concentrations through the electrode to draw the standard curve.

[0103] Then the reaction cup is cleaned and waiting to be used for detection.

[0104] S2. Sample fluoride.

[0105] The membrane clip storage and conveying mechanism conveys the membrane clips in the two membrane clip storage bins onto the upper membrane clip tray and the lower membrane clip tray respectively. The pressing component of the double-layer sampling mechanism presses the membrane clip assembly. After starting the fan, the sampled gas enters the sampling tube, and after being collected by the upper layer membrane clip and the lower layer membrane clip in sequence, it is discharged from the measuring device through the exhaust duct by the fan; the fluoride in the sampled gas adheres to the two membrane sheets.

[0106] S3. Extraction of fluoride. After the filter membrane adsorbed with fluoride is sheared by the laser cutting mechanism, it falls into the first reaction cup and the second reaction cup of the reactor; the controller controls the lifting motor in the switching mechanism to lift the cup plug body upward to seal the waste liquid pipe, so as to form a reaction space in the inner cavity of the reaction cup; then the controller controls the horizontal drive motor to act, and sequentially moves the first reaction cup and the second reaction cup to the position below the liquid injection head, and then the controller starts the liquid injection head 732 to inject relevant reagents into the first reaction cup and the second reaction cup respectively.

[0107] The controller starts the circulating water pump 753 to pump the circulating medium in the water tank into the reactor 731; then, the controller controls the ultrasonic oscillator 739 to work to provide a vibration frequency; at the same time, the stirring motor is started to stir the reaction solution and the filter membrane fragments in the reaction cup, so as to ensure that the solution in the reaction cup can fully extract the fluoride on the sampling filter membrane.

[0108] S4. Determination of fluoride. The controller first controls the lifting module to lift the electrode; then, by controlling the horizontal movement motor to drive the reactor to move, the first reaction cup is located below the electrode, and then the controller controls the lifting module to move the electrode downward into the first reaction cup, and the electrode measures the solution in the reaction cup; after the measurement is completed, the electrode feeds back the measurement result to the controller, and the controller analyzes the measurement result. Then, the determination of fluoride in the second reaction cup is sequentially completed.

[0109] After the measurement is completed, the controller controls the lifting motor to act, drives the cup plug body and the cup plug cover to descend, opens the waste liquid pipe inlet, and connects the reaction cup and the waste liquid pipe. At this time, the reaction solution with filter membrane fragments all flows into the water tank through the waste liquid pipe and will not remain between the cup plug body and the inner wall of the reaction cup, preventing the occurrence of liquid leakage during re - use.

[0110] After the measurement is completed, the electrode will upload the measured voltage value to the controller, and the controller calculates the concentration of fluoride in the filter membrane according to the standard curve drawn in the first step.

[0111] The membrane clip completed by the laser cutting mechanism will be sent to the waste membrane clip collection bin for collection under the push of the membrane clip storage and conveying mechanism.

Claims

1. Improved fluoride automatic determination device, comprising a frame (1) and a controller (2), characterized in that: A double-layer sampling mechanism (4) for fluoride sampling, a laser cutting mechanism (5) for shearing filter membranes, a reaction detection mechanism (7) for performing fluoride extraction reactions and detections, and a liquid supply mechanism (6) for providing reaction reagents for the reaction detection mechanism are provided on the frame; a membrane clip storage and conveying mechanism (3) for storing and sequentially conveying membrane clips to the double-layer sampling mechanism, the laser cutting mechanism (5), and the reaction detection mechanism (7) is further provided on the frame; the output end of the controller is respectively connected to the controlled ends of the double-layer sampling mechanism, the laser cutting mechanism (5), the reaction detection mechanism (7), and the membrane clip storage and conveying mechanism (3); The reaction detection mechanism (7) includes a standard solution component, a reaction component, and a determination component provided on the frame; a reaction moving component for controlling the horizontal movement of the reaction component is further provided on the frame, a water tank component for providing a circulating medium for the reaction component and recovering reaction waste liquid is provided between the reaction component and the reaction moving component, and the reaction component discharges waste liquid into the water tank component in a plunger side liquid discharge manner; the output end of the controller is respectively connected to the controlled ends of the standard solution component, the reaction component, the determination component, the reaction moving component, and the water tank component; The reaction moving component includes a horizontal mounting frame (721) horizontally and fixedly mounted on the frame, a horizontal driving motor (722) is fixedly provided on one side of the horizontal mounting frame, the output end of the horizontal driving motor is shaft-connected to a lead screw lying horizontally in the horizontal mounting frame and located below the reaction component, and a moving block threadedly fitted with the lead screw is further slidably provided in the horizontal mounting frame (721); the water tank component is fixedly provided on the moving block; The water tank component includes a water tank (75) fixedly provided on the moving block, and the top of the water tank is provided with an open mouth; a circulating water pump (753) communicating with the inner cavity of the water tank and used for conveying the circulating medium to the reaction component is fixedly provided on an outer wall of one side of the water tank, and a liquid discharge pump (754) is provided on an outer wall of the other side of the water tank; a stainless steel filter screen (752) is erected on the top of the water tank; The reaction component includes a reactor (731), a liquid injection head (732), a plunger-type switching mechanism, an ultrasonic oscillator (739), and a stirring mechanism; a vertical mounting frame is further fixedly arranged on the moving block, the back of the vertical mounting frame is fixedly connected to a water tank (75), and a reactor (731) communicating with the water tank and used for receiving the circulating medium conveyed by the water tank is fixedly arranged on the top end surface of the vertical mounting frame. The reactor (731) is a cuboid structure with a cavity inside. An ultrasonic oscillator (739) for providing a vibration frequency for the circulating medium in the reactor is mounted on the outer wall of the reactor (731); a liquid inlet pipe (7311) for inputting the circulating medium into the inner cavity is arranged at the bottom of the reactor (731), and the liquid inlet pipe (7311) is communicated with a pipeline connected to the liquid outlet of a circulating water pump (753). The liquid inlet of the circulating water pump (753) is communicated with the inner cavity of the water tank through a pipeline; a first reaction cup and a second reaction cup (734) which are vertical and not communicated with the inner cavity of the reactor are horizontally arranged side by side in the reactor (731). Waste liquid pipes (735) facing the stainless steel filter screen (752) at the top of the side water tank are respectively arranged on the lower side walls of the first reaction cup and the second reaction cup (734) extending out of the bottom of the reactor; a plunger-type switching mechanism which is vertically upward and the top of which extends into the lower parts of the first reaction cup and the second reaction cup (734) and is used for controlling the opening and closing of the waste liquid pipe is arranged on the vertical mounting frame.

2. The improved fluoride automatic measuring device according to claim 1, characterized in that: The membrane clip storage and conveying mechanism (3) includes a membrane clip storage bin (31) vertically mounted on the machine frame. One end face of the membrane clip storage bin (31) is open. An elevating module (32) for lifting the membrane clips stored in the membrane clip storage bin to the discharge port is arranged on the machine frame behind the membrane clip storage bin (31). A discharge tray (35) for carrying a single membrane clip is arranged on the machine frame on one side of the top of the membrane clip storage bin. A transverse translation module (33) for horizontally pulling the membrane clip from the discharge port of the membrane clip storage bin to the discharge tray (35) is arranged on the machine frame above the discharge tray. A longitudinal translation module (34) for pushing the membrane clip on the discharge tray (35) to the double-layer sampling mechanism is arranged on the machine frame behind the discharge tray (35); the controlled ends of the elevating module (32), the transverse translation module (33), and the longitudinal translation module (34) are respectively connected to the output end of the controller.

3. The improved fluoride automatic determination device according to claim 2, wherein: The elevating module (32) includes an elevating support (321) fixedly arranged on the machine frame. An elevating drive motor (323) is fixedly arranged at the top end of the elevating support (321). An elevating lead screw (322) is installed between the upper and lower end plates of the elevating support (321) through bearings. The top end of the elevating lead screw (322) is connected to the output shaft of the elevating drive motor; an elevating block (324) is threadedly connected to the elevating lead screw; a membrane clip supporting plate (325) which is horizontally arranged in the membrane clip storage bin and is connected to the elevating block and moves up and down in the membrane clip storage bin driven by the elevating block is arranged in the membrane clip storage bin.

4. The improved fluoride automatic measuring device according to claim 3, characterized in that: Two film storage bins are symmetrically arranged on the left and right of the frame. A set of lifting modules (32) are respectively arranged corresponding to the two film storage bins. The horizontal translation module (33) is located above the space between the two film storage bins. The discharge tray (35) is located between the discharge ports (326) of the two film storage bins. The longitudinal translation module (34) is located behind the discharge tray (35) between the two film storage bins.

5. The improved fluoride automatic measuring device according to claim 1, characterized in that: The double-layer sampling mechanism (4) includes a top sealing assembly (42) and a mounting plate (43) that are arranged parallel to each other up and down. The mounting plate (43) is fixedly arranged on the frame. The top sealing assembly (42) and the mounting plate (43) are fixedly connected by four linear optical axes (414) fixedly arranged at the corners. A vertical sampling tube (41) is communicatively arranged at the center of the top sealing assembly (42). A bottom sealing assembly (44) sleeved on the linear optical axis (414) is further arranged between the top sealing assembly (42) and the mounting plate (43). A membrane clip assembly for clamping the membrane clip is arranged between the top sealing assembly (42) and the bottom sealing assembly (44). The membrane clip assembly is a double-layer membrane clip arranged side by side up and down. A driving motor (47) is fixedly arranged on the mounting plate. The output end of the driving motor (47) is connected with a driving assembly for driving the bottom sealing assembly to move up and down to open and close the membrane clip assembly. A through hole is opened at the center of the mounting plate (43). A suction duct (45) coaxial with the sampling tube is passed through the through hole. The top end of the suction duct (45) is communicatively connected with the center of the bottom sealing assembly (44). The bottom end of the suction duct (45) is connected with a blower (46) through a hose.

6. The improved fluoride automatic determination device according to claim 5, characterized in that: The membrane clip assembly includes an upper membrane clip tray (412) and a lower membrane clip tray (411) arranged side by side up and down. The lower membrane clip tray (411) is arranged on the top end surface of the bottom sealing assembly (44) through four second springs (413). An intermediate sealing assembly (420) is fixedly arranged on the top end surface of the lower membrane clip tray (411). The upper membrane clip tray (412) is arranged on the top end surface of the intermediate sealing assembly (420) through four second springs (413). Through holes corresponding to the sizes of the air flow holes on the membrane clip and for allowing the sampling gas to flow from the sampling tube (41) to the suction duct (45) are opened at the centers of the top sealing assembly (42), the intermediate sealing assembly (420), and the bottom sealing assembly (44).

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