Hybrid double-layer spiral reaction chamber, single-layer spiral trap and atmospheric hydrogen peroxide concentration measuring device

Abstract

The mixed type double-layer spiral reaction chamber comprises a first reaction chamber and a second reaction chamber which are sequentially arranged in the sample injection direction, and the first reaction chamber comprises a first double-layer spiral pipe composed of a first spiral pipe and a second spiral pipe which are arranged in a winding mode; the second reaction chamber comprises a second double-layer spiral pipe consisting of a third spiral pipe and a fourth spiral pipe which are wound with each other; the first spiral tube is detachably connected with the third spiral tube, and the second spiral tube is detachably connected with the fourth spiral tube, so that second channels for detecting the peroxide concentration in the sample are respectively formed. Different from an existing double-channel detector, the hybrid double-layer spiral reaction chamber provided by the utility model has the advantages that the common part of the two channels is increased to the maximum extent through the double spiral channels, the sensitivity of equipment is improved, the use of parts and the volume and weight of the equipment are reduced, and the portability and the real-time detection sensitivity of the equipment are improved.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of environmental monitoring, and particularly relates to a mixed double-layer spiral reaction chamber. BACKGROUND

[0002] Atmospheric hydrogen peroxide is an important oxidant in the troposphere, has high reactivity and oxidation capacity, and its concentration level can be regarded as one of indicators of atmospheric oxidizability to some extent, and has a key influence on the formation of tropospheric O3. Hydrogen peroxide is an important factor leading to acid deposition and the increase of secondary aerosol concentration, affects the ecological system and climate change, in addition, hydrogen peroxide also has biological toxicity and human exposure risk, can reduce the content of chlorophyll in cells and thus affect the normal growth of plants, and when aerosol containing hydrogen peroxide enters the human respiratory system, can also damage human lung epithelial cells and cause diseases such as asthma and cancer. Therefore, it is of great significance to realize accurate measurement of atmospheric hydrogen peroxide and understand the concentration change of atmospheric hydrogen peroxide in the troposphere.

[0003] At present, there is a lack of online analysis equipment suitable for field observation and capable of reliable measurement of hydrogen peroxide, which makes it difficult to realize complete online measurement of hydrogen peroxide, and there are problems such as insufficient quantitative precision and insufficient stability. Therefore, it is particularly important to develop online analysis instruments for atmospheric hydrogen peroxide, which will help to realize reliable real-time monitoring and research on the change law of atmospheric hydrogen peroxide.

[0004] The existing online analysis technology for atmospheric hydrogen peroxide is mainly based on spectroscopy, chemiluminescence and fluorescence. The spectroscopy has a high detection limit and is not suitable for measuring atmospheric environmental concentration, and the equipment is expensive and has high maintenance cost in the later period, which is not conducive to popularization. The chemiluminescence method is simple but has the disadvantage of low sensitivity. The fluorescence spectrophotometry is often used for determination of low-concentration hydrogen peroxide content, has the advantages of good selectivity, high sensitivity and continuous operation. However, the equipment is large in size and high in price, for example, the AL2021 type hydrogen peroxide online analyzer produced by Aero-Laser Company in Germany is this method. The current double-channel measurement adopts complete parallel detection of two channels, and the parts used are twice as much as those of a single channel, resulting in increased equipment cost, complex instrument gas circuit, increased consumables, difficult maintenance in the later period, and limitation of popularization.

[0005] Therefore, in order to save cost, simplify the pipeline and facilitate flexible use, the application provides a mixed double-layer spiral reaction chamber, a single-layer spiral trapping trap, and based on this, provides a measurement device for atmospheric hydrogen peroxide concentration with trapping-reaction-detection integration. CONTENT OF THE INVENTION

[0006] In order to solve the problems in the prior art, the purpose of the present application is to provide a hydrogen peroxide reaction device, a hydrogen peroxide trapping device and a trapping-reaction-detection integrated measuring device, which maximizes the use of parts and cost of the detection device, improves the commonality of the double-channel detection, reduces the discrimination effect, and increases the monitoring sensitivity of the device. Based on the single-layer spiral trapping trap operating at low temperature and the mixed double-layer spiral reaction chamber operating at high temperature, the cold pipe and the heat pipe are used to conduct cooling / heating from the upper end to the lower end of the two device pipelines, without the need for insulation and real-time observation of the pipeline state in the pipe, ensuring the uniform and constant temperature of the trapping trap and the reaction chamber, improving the trapping efficiency and reaction degree; the entire measuring device is small in design and compact in structure, and can be used for online continuous monitoring of hydrogen peroxide.

[0007] Specifically, the present application relates to the following aspects:

[0008] 1. A mixed double-layer spiral reaction chamber, comprising: a first reaction chamber and a second reaction chamber arranged in sequence in the sampling direction, the first reaction chamber comprising a first double-layer spiral pipe composed of a first spiral pipe and a second spiral pipe arranged in mutual winding, and the second reaction chamber comprising a second double-layer spiral pipe composed of a third spiral pipe and a fourth spiral pipe arranged in mutual winding; the first spiral pipe and the third spiral pipe are detachably connected to form a first channel for detecting the concentration of peroxide in a detection sample; and the second spiral pipe and the fourth spiral pipe are detachably connected to form a second channel for detecting the concentration of peroxide in a detection sample.

[0009] 2. The mixed double-layer spiral reaction chamber according to item 1, wherein the second reaction chamber comprises a plurality of heaters and a plurality of heat pipes; the plurality of heaters are arranged at the lower end of the second double-layer spiral pipe, and the plurality of heat pipes extend from the plurality of heaters along the central spiral axis of the second double-layer spiral pipe to the upper end of the second double-layer spiral pipe at the middle and / or outer edge of the second double-layer spiral pipe, so as to maintain the overall temperature of the second double-layer spiral pipe constant; when the number of heat pipes extending along the central spiral axis of the second double-layer spiral pipe to the upper end of the second double-layer spiral pipe at the middle of the second double-layer spiral pipe is not less than 2, the heat pipes extending along the central spiral axis of the second double-layer spiral pipe to the upper end of the second double-layer spiral pipe at the middle of the second double-layer spiral pipe are uniformly distributed; the heater makes the temperature of the second reaction chamber 30-45℃.

[0010] 3. The hybrid double-layer spiral reaction chamber according to item 1, wherein the first spiral tube and the second spiral tube are made of quartz glass or polytetrafluoroethylene; the inner diameter of the first spiral tube and the second spiral tube is 1-1.2 mm; the length of the first spiral tube and the second spiral tube is 30-90 cm; the number of turns of the first spiral tube and the second spiral tube is 6-10 turns; and the spiral diameter of the first spiral tube and the second spiral tube after winding is 10-15 mm; the third spiral tube and the fourth spiral tube are made of quartz glass or polytetrafluoroethylene; the inner diameter of the third spiral tube and the fourth spiral tube is 1.2-1.5 mm; the length of the third spiral tube and the fourth spiral tube is 90-130 cm; the number of turns of the third spiral tube and the fourth spiral tube is 10-15 turns; and the spiral diameter of the third spiral tube and the fourth spiral tube after winding is 15-20 mm.

[0011] 4. The hybrid double-layer spiral reaction chamber according to item 2, wherein the number of the plurality of heat-conducting tubes is 3-8; preferably, the number of the plurality of heat-conducting tubes is 8; the plurality of heat-conducting tubes are made of one or more than one of pure copper, brass, combined heat pipe or nichrome heating wire; and the length of the heat-conducting tube is 120-150 cm, and the width of the heat-conducting tube is 1-3 mm; the second reaction chamber further comprises a patch temperature sensor.

[0012] 5. A single-layer spiral trapping trap, comprising: a fifth spiral tube, a plurality of refrigeration components and a plurality of cold pipes, the plurality of refrigeration components are arranged at the lower end of the fifth spiral tube, and the plurality of cold pipes respectively extend from the plurality of refrigeration components along the central spiral axis of the fifth spiral tube to the upper end of the fifth spiral tube in the middle and / or outer edge of the fifth spiral tube to keep the overall temperature of the fifth spiral tube constant; when the number of cold pipes extending along the central spiral axis of the fifth spiral tube to the upper end of the fifth spiral tube in the middle of the fifth spiral tube is not less than 2, the cold pipes extending to the upper end of the fifth spiral tube in the middle of the fifth spiral tube are uniformly distributed; the refrigeration components make the temperature of the fifth spiral tube be 0-10℃.

[0013] 6. The single-layer spiral trapping trap according to item 5, wherein the inner diameter of the fifth spiral tube is 1.8-2.2 mm; the length of the fifth spiral tube is 40-100 cm; the number of turns of the fifth spiral tube is 10-16 turns; and the spiral diameter of the fifth spiral tube is 15-20 mm.

[0014] 7. The single-layer spiral trapping trap according to item 5, wherein the number of the plurality of cold pipes is 3-8; preferably, the number of the plurality of cold pipes is 8; the plurality of cold pipes are made of pure copper and / or brass; and the length of the cold pipe is 120-150 cm, and the width of the cold pipe is 1-3 mm; the single-layer spiral trapping trap further comprises a patch temperature sensor.

[0015] 8. The atmospheric hydrogen peroxide concentration measuring device comprises a trapping module, a reaction module, a detection module and a calculation module; the trapping module is connected with the input end of the reaction module by pipeline, used for inhaling a detection sample from the atmosphere and trapping peroxide in the detection sample to obtain a trapping liquid sample containing the detection sample; the trapping module divides the trapping liquid sample into sample A and sample B and respectively sends them to the reaction module, which respectively processes them and respectively obtains two fluorescence reaction liquid samples through fluorescence reaction after processing; the detection module is connected with the output end of the reaction module by pipeline, used for receiving the two fluorescence reaction liquid samples and respectively detecting the total concentration of peroxide in the two fluorescence reaction liquid samples; the calculation module calculates the hydrogen peroxide concentration in the detection sample based on the total concentration of peroxide in the two fluorescence reaction liquid samples.

[0016] 9. The atmospheric hydrogen peroxide concentration measuring device according to item 8, wherein the trapping module comprises an absorption liquid pump, a liquid flow controller, a gas three-way valve, a single-layer spiral trapping trap according to any one of items 5-7 and a gas-liquid separation unit, wherein the upper end of the single-layer spiral trapping trap is respectively connected with the gas three-way valve and the absorption liquid pump by pipeline; the gas three-way valve introduces the detection sample and / or zero gas sample into the single-layer spiral trapping trap; the absorption liquid pump introduces the absorption liquid into the single-layer spiral trapping trap and forms an absorption liquid film on the inner wall of the fifth spiral pipe to trap the peroxide in the detection sample and obtain the trapping liquid sample; the lower end of the single-layer spiral trapping trap is connected with the gas-liquid separation unit by pipeline, and the gas-liquid separation unit separates the trapping liquid sample and the remaining gas, and divides the trapping liquid sample into sample A and sample B to be respectively sent to the reaction module.

[0017] 10. The atmospheric hydrogen peroxide concentration measuring device according to item 8, wherein the reaction module comprises a mixed double-layer spiral reaction chamber according to any one of items 1-4; the first spiral pipe respectively obtains sample A and parallel liquid by peristaltic pump and mixes sample A and parallel liquid to obtain mixed solution A, the second spiral pipe respectively obtains sample B and reaction liquid by peristaltic pump and mixes sample B and reaction liquid to obtain mixed solution B; the third spiral pipe respectively obtains mixed solution A and derivative liquid from the lower end of the first spiral pipe by peristaltic pump and mixes mixed solution A and derivative liquid to obtain fluorescence reaction liquid sample A; the fourth spiral pipe respectively obtains mixed solution B and derivative liquid from the lower end of the second spiral pipe by peristaltic pump and mixes mixed solution B and derivative liquid to obtain fluorescence reaction liquid sample B.

[0018] Advantages

[0019] The mixed double-layer spiral reaction chamber, single-layer spiral trapping trap and atmospheric hydrogen peroxide concentration measuring device provided by the application have the following technical effects:

[0020] 1.The measuring device for atmospheric hydrogen peroxide concentration provided in the application utilizes the double-channel fluorescence method to measure hydrogen peroxide, which has the advantages of good selectivity and high sensitivity, but the general measuring equipment has complex pipelines, and the equipment on the market can only apply the capture, reaction and measurement method of the whole double-channel design mode; in addition, the existing equipment uses complex parts, resulting in high overall cost of the equipment, which limits the popularization of the detection technology. Therefore, the measuring device provided in the application optimizes the structure design, separates the pipeline after entering the mixed double-layer spiral reaction chamber, and integrates the capture pipeline before the reaction chamber into one, which not only simplifies the pipeline, but also effectively avoids the use of a large number of equipment parts, thereby reducing the volume and manufacturing cost; in addition, the measuring device provided in the application also increases the commonality between the double channels for the reaction of the to-be-detected substance and the detection reagent, increases the measurement parallelism, avoids the discrimination effect and affects the measurement accuracy.

[0021] 2.The measuring device for atmospheric hydrogen peroxide concentration provided in the application designs an integrated single-layer spiral capture trap, in order to ensure the capture efficiency, a contact type refrigeration structure is provided, a rapid cooling pipe is arranged in parallel in the upstream, middle and downstream of the sample flow direction of the single-layer spiral capture trap, a refrigeration component is arranged at one end of the rapid cooling pipe, the temperature is quickly transmitted to the single-layer spiral capture trap by the high-efficiency cooling property of the rapid cooling pipe, the uniformity of the temperature in the capture trap is ensured, and the reduction of the capture efficiency caused by the temperature difference is avoided; in addition, the material of the single-layer spiral capture trap is quartz glass, the gas-liquid state in the capture trap can be observed in real time without thermal insulation measures, and faults are effectively prevented.

[0022] 3.The measuring device for atmospheric hydrogen peroxide concentration provided in the application designs a mixed double-layer spiral reaction chamber with a double-spiral channel configuration, the double-channel reaction chamber is integrated in parallel, which not only ensures the parallelism between the double channels, but also effectively reduces the volume of the device occupied by the catalase decomposition reaction and the fluorescence reaction part; in addition, the measuring device provided in the application also designs a heating structure for uniformly heating the mixed double-layer spiral reaction chamber, the heater is uniformly arranged in parallel at multiple positions of the reaction channel along the upstream, middle and downstream of the detection sample flow direction to effectively provide the high-temperature condition required by the double-channel reaction, ensure the uniform distribution of the internal temperature of the mixed double-layer spiral reaction chamber, avoid the reduction of the reaction efficiency caused by the temperature difference and the discrimination effect between the double channels, so as to produce high-quality fluorescent substances and be used for hydrogen peroxide concentration detection. BRIEF DESCRIPTION OF DRAWINGS

[0023] Figure 1 The structure of the mixed double-layer spiral reaction chamber according to the embodiment of the application is shown in the figure.

[0024] Figure 2Fig. 1 shows a structural schematic diagram of a double-layer spiral trapping device according to an embodiment of the present application.

[0025] Figure 3 Fig. 4 shows a structural schematic diagram of a device for measuring atmospheric hydrogen peroxide concentration according to an embodiment of the present application. DETAILED DESCRIPTION

[0026] The present application is further illustrated by the following examples, which are not intended to limit the present application in any way.

[0027] Unless otherwise defined, all technical and scientific terms used in this specification have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present application, illustrative methods and materials are described below. However, if there is a conflict between the definitions in this specification and those in the materials, methods, and examples, the definition in this specification controls. Unless otherwise indicated, materials, methods, and examples are illustrative only and not intended to be limiting.

[0028] DEFINITIONS

[0029] Trapping device

[0030] A trapping device is a device used for trapping and separating target compounds. When a gas containing target compounds passes through the trapping device, the target compounds are absorbed by ions or molecules in a solution previously configured in the trapping device, thereby being enriched and trapped in the solution. As the reaction proceeds, the target compounds can be precipitated or discharged with the solution, thereby improving the purity of the gas or obtaining an absorption solution of the target compounds.

[0031] Derivatization solution

[0032] A derivatization solution is a reagent that can chemically react with specific components in a sample, thereby improving the detection sensitivity and accuracy of target compounds by generating new, easily detectable compounds, i.e., derivative products. For some compounds that are highly polar, have high boiling points, poor thermal stability, or weak ultraviolet absorption, direct detection can be very difficult. Through derivatization treatment, they can be converted into compounds that are less polar, volatile, thermally stable, or have significant ultraviolet absorption, thereby improving their detectability in chromatographic or spectral analysis. Through derivatization treatment, the signal intensity in mass spectrometric analysis can be significantly improved, thereby improving the detection sensitivity.

[0033] Zero gas sample

[0034] A gas sample used to adjust or set the minimum scale (i.e. zero point) of a gas analyzer. When this gas sample enters a particular analyzer, the analyzer should show a reading of zero or near zero. To ensure the accuracy of the baseline measurement, the zero gas sample should not contain any of the components to be measured or any impurities that can interfere with the measurement, but can contain components that are not relevant to the measurement.

[0035] At present, the measurement of atmospheric hydrogen peroxide on the market mainly adopts the double-channel fluorescence measurement method of peroxide. Specifically, peroxide reacts with fluorescent agent under the action of peroxidase to produce dimer with fluorescence, so a double-channel measurement method is adopted, that is, one channel determines the amount of total peroxide according to the fluorescence signal generated by total peroxide, and the other channel adds peroxidase which can quickly and completely destroy hydrogen peroxide in peroxide in advance, and the hydrogen peroxide content can be obtained by subtracting the two detection results according to the fluorescence signal generated by total peroxide after reaction and the content of organic peroxide after removing hydrogen peroxide. The method is simple, selective and sensitive, but the double-channel needs more pipelines and components, resulting in expensive overall cost and large volume of detection equipment, which limits its popularization and application.

[0036] Based on the technical problems in the field of real-time detection of hydrogen peroxide at present, the application provides a mixed double-layer spiral reaction chamber based on the double-channel fluorescence spectrophotometric method for fluorescence characterization of hydrogen peroxide, as shown in Figure 1 , and a single-layer spiral trapping trap, as shown in Figure 2 , for respectively performing fluorescence reaction treatment and liquid phase trapping of atmospheric hydrogen peroxide. The mixed double-layer spiral reaction chamber according to the embodiment of the application is shown in Figure 1 , which comprises a first reaction chamber and a second reaction chamber arranged in the sampling direction. The first reaction chamber is used for hydrogen peroxidase hydrolysis treatment of liquid phase samples containing dissolved hydrogen peroxide. Therefore, the first reaction chamber is designed to include a first double-layer spiral pipe composed of a first spiral pipe and a second spiral pipe arranged by interwinding. Two liquid phase samples with the same hydrogen peroxide content and the same mass of substances that can react with hydrogen peroxidase, or without substances that can react with hydrogen peroxidase, can be treated in the first reaction chamber and the second reaction chamber respectively to obtain samples with different hydrogen peroxide contents.

[0037] In some possible embodiments, in order to ensure that the liquid sample can be decomposed with higher efficiency after mixing with catalase in the first reaction chamber, the size of the first double-layer spiral tube is designed very strictly. Since the first reaction chamber and the second reaction chamber are arranged in sequence in the mixed double-layer spiral reaction chamber, and in order to ensure that the volume of the mixed double-layer spiral reaction chamber is as small as possible, the length of the first double-layer spiral tube needs to be further shortened relative to the enzyme hydrolysis channel of the existing double-channel instrument, which may cause the problem of insufficient enzyme hydrolysis. In the first spiral tube or the second spiral tube, the liquid sample and the catalase solution cannot be fully contacted or the contact time is not guaranteed, which can be achieved by increasing the number of winding turns of the first double-layer spiral tube to make the liquid sample pass through a long enough distance in the first reaction chamber; in the case of a certain number of winding turns, the spiral diameter of the first double-layer spiral tube can be further increased to prolong the enzyme hydrolysis time.

[0038] However, this way of improving the decomposition of hydrogen peroxide can make up for the problem of insufficient reaction caused by the reduction of the volume of the reaction chamber, but usually the second reaction chamber needs to be provided with a heating component to provide reaction conditions for the fluorescence reaction of peroxide. If the spiral diameter of the first double-layer spiral tube is greater than the diameter of the second double-layer spiral tube heated in the second reaction chamber, the first double-layer spiral tube may be unevenly heated. The optimum reaction temperature of catalase is 30-40℃, and an excessively large spiral diameter may cause the temperature of the inner edge and the outer edge of the first double-layer spiral tube to be uneven, and the efficiency of catalase hydrolysis of hydrogen peroxide of the liquid sample will be affected.

[0039] In addition, the axial propulsion force of the liquid in the spiral tube is inversely proportional to the tube diameter, and the increase of the number of winding turns will affect the flow state and kinetic parameters of the absorbing liquid, for example, increasing the pitch will weaken the turbulence intensity in the tube to a certain extent, and increasing the tube diameter will significantly increase the intensity of the turbulence of the fluid in the tube. These changes will eventually affect the heat transfer performance of the absorbing liquid. Therefore, the length, number of winding turns and diameter of the first double-layer spiral tube and the second double-layer spiral tube need to maintain a certain proportion, so that the reaction efficiency of the liquid sample in the spiral reaction chamber can be kept at an optimal level, so that the enzyme hydrolysis and fluorescence reaction that usually need longer straight tubes can be completed in the spiral tube with limited axial length.

[0040] Another problem to be noted is that in order to mix the liquid sample and the catalase in the first reaction chamber sufficiently, the inner diameter of the first spiral tube and the second spiral tube should also be able to provide sufficient space for mixing the two solutions, and therefore, the inner diameter of the first spiral tube and the third spiral tube should also maintain a preferred ratio with the number of turns and the spiral diameter, so that the first double-layer spiral tube can ensure the efficient progress of the catalase hydrolysis treatment. In this way, the first double-layer spiral tube forms a circulating flow of the liquid sample and the reactant in the first spiral tube and the second spiral tube by rotation and centrifugal force, ensuring that the mixed solution is evenly distributed in the first spiral tube or the second spiral tube, avoiding the dead angle and stratification phenomenon of the mixed solution in the container due to turbulent flow, thereby accelerating the enzymatic hydrolysis speed, shortening the enzymatic hydrolysis time, and achieving the purpose of reducing the volume.

[0041] In some possible embodiments, the inner diameter of the first spiral tube and the second spiral tube is set to 1-1.2 mm, and the length of the first spiral tube and the second spiral tube is set to 30-90 cm to ensure that the volume is reduced as much as possible while ensuring the sufficient progress of the enzymatic hydrolysis; the number of turns of the first spiral tube and the second spiral tube is set to 6-10 turns, and the spiral diameter of the first spiral tube and the second spiral tube after winding is 10-15 mm, so that the temperature distribution of the first double-layer spiral tube as a whole is uniform, avoiding the influence of high / low temperature in some positions on the enzyme activity. In particular, in an advantageous embodiment, the length of the first spiral tube and / or the second spiral tube is preferably 90 cm, and on this basis, it is further preferred that the number of turns of the first spiral tube and / or the second spiral tube is 9 turns, and the inner diameter is 1.1 mm.

[0042] It can be understood that the material of the first spiral tube and the second spiral tube can be advantageously selected from quartz glass or polytetrafluoroethylene, and in particular, quartz glass is selected, so that the experimenter or operator can observe the reaction of the liquid sample and the gas-liquid situation in real time when using the mixed double-layer spiral reaction chamber according to the embodiments of the present application through the first spiral tube and the second spiral tube, avoiding the entry of bubbles and causing the mutation of the subsequent measurement signal. In addition, the functions of the first spiral tube and the second spiral tube can be replaced with each other, for example, adding catalase solution in the first spiral tube for catalase hydrolysis, adding deionized water in the second spiral tube to not consume hydrogen peroxide, or adding catalase solution in the second spiral tube for catalase hydrolysis, and adding deionized water in the first spiral tube to not consume hydrogen peroxide, which can be adjusted according to the actual situation.

[0043] After the liquid sample and the mixed solution of the reaction solution, such as the catalase solution, and the parallel liquid, such as the ultrapure water, are obtained in the first reaction chamber, the derivative solution is only needed to be added into the mixed solution to establish the standard curve of the peroxide concentration of the liquid sample by detecting the fluorescence spectrum of the fluorescent dye in the derivative solution and to calculate the peroxide concentration. The fluorescence reaction process can be carried out immediately in the second reaction chamber, which comprises a second double-layered spiral tube composed of a third spiral tube and a fourth spiral tube arranged in a mutual winding manner as a double spiral channel for the reaction. It can be understood that the two reaction channels of the second reaction chamber need to be provided with balanced and stable reaction temperature during the fluorescence reaction, which requires the second double-layered spiral tube to be heated uniformly.

[0044] It can be understood that, in the case where the heating structure is determined along the sample introduction direction, the heating distance of the spiral structure in the direction perpendicular to the sample introduction direction is periodically changed, for example, in a sinusoidal distribution, and therefore the second double-layered spiral tube is more likely to have a partially uneven temperature than the existing complete double-channel reaction channel. Therefore, the spiral diameter of the second double-layered spiral tube should not be too large, and the number of windings should not be too dense, but a certain duty cycle should be maintained between each winding, which is different from the second double-layered spiral tube. Therefore, in some possible embodiments, the length of the third spiral tube and the fourth spiral tube is set to be between 90-130 cm to ensure sufficient fluorescence reaction while minimizing the overall length of the second double-layered spiral tube; after the length is determined, the number of windings of the third spiral tube and the fourth spiral tube can be set to be between 10-15 turns to ensure sufficient fluorescence reaction of the liquid sample and the derivative solution in the tube.

[0045] Further, in order to maintain a certain distance between each winding of the second double-layered spiral tube to ensure that each winding is heated uniformly in the direction perpendicular to the sample introduction direction, after the length and the spiral diameter are determined, the spiral diameter of the third spiral tube and the fourth spiral tube after winding can be set to be between 15-20 mm in combination with the size of the spiral diameter, which can ensure that the radial area of each winding is not too large to expand the volume of the entire mixed double-layered spiral reaction chamber, and also allows the heat emitted by the heating component to be better conducted through the air at the non-contact part of each winding. Finally, the inner diameter of the third spiral tube and the fourth spiral tube can be set to be between 1.2-1.5 mm to ensure that the liquid sample and the derivative solution form a circulating flow in the tube, and the reaction process is more efficient than the complete double-channel instrument. In particular, in an advantageous embodiment, the length of the third spiral tube and / or the fourth spiral tube is preferably 120 cm, and on this basis, it is further preferred that the number of windings of the third spiral tube and / or the fourth spiral tube is 13 turns and the inner diameter is 1.5 mm.

[0046] It can be understood that the third spiral tube and the fourth spiral tube can be made of quartz glass or polytetrafluoroethylene, and in particular, the third spiral tube and the fourth spiral tube can also be made of quartz glass, so that the experimenter or operator can observe the reaction of the liquid sample and the derivatization liquid and the gas-liquid condition in real time through the third spiral tube and the fourth spiral tube when using the mixed double-layer spiral reaction chamber according to the embodiment of the present application, thereby avoiding bubbles from interfering with the reaction and causing sudden changes in the measurement signal. In addition, the functions of the third spiral tube and the fourth spiral tube can be replaced with each other, for example, adding a sample that has been decomposed by hydrogen peroxide into the third spiral tube for fluorescence reaction, adding a sample that has not been decomposed by hydrogen peroxide into the fourth spiral tube for fluorescence reaction, or adding a sample that has been decomposed by hydrogen peroxide into the fourth spiral tube for fluorescence reaction, and adding a sample that has not been decomposed by hydrogen peroxide into the third spiral tube for fluorescence reaction. The use of the two spiral tubes can be adjusted according to the actual situation.

[0047] In some possible embodiments, the first spiral tube and the third spiral tube together form a first channel for detecting the concentration of peroxide in the liquid sample, and the second spiral tube and the fourth spiral tube together form a second channel for detecting the concentration of peroxide in the liquid sample. The hydrogen peroxide contained in the liquid sample is treated differently in the first channel and the second channel to determine the amount of hydrogen peroxide reduced in one of the channels by the difference in fluorescence intensity of the derivatization liquid, thereby further determining the concentration of hydrogen peroxide in the liquid sample. An advantageous improvement is that the first spiral tube and the third spiral tube are detachably connected, and the second spiral tube and the fourth spiral tube are also detachably connected, so that when bubbles or any unexpected situation occur in the solution in the mixed double-layer spiral reaction chamber, the operation can be stopped in time to correct or replace the parts, thereby avoiding equipment failure. In addition, the mixed double-layer spiral reaction is easier to maintain and transport, which increases its environmental suitability.

[0048] According to the single-layer spiral trapping trap of the embodiment of the present application, as shown in Figure 2 The fifth spiral tube can be composed of only one spiral tube, i.e., the fifth spiral tube, and the spiral structure of the fifth spiral tube can improve the efficiency of trapping gas-phase peroxide. In order to better achieve the function of trapping peroxide and at the same time consider reducing the volume of the device as much as possible, the length of the fifth spiral tube can be set to be between 40-100 cm, so as to ensure that after the absorption liquid forms an absorption liquid film on the inner wall of the tube, the gas-phase peroxide can be fully absorbed after hitting the absorption liquid film by molecular diffusion. The inner diameter of the fifth spiral tube can be set to be between 1.8-2.2 mm, so as to ensure the efficient formation of the absorption liquid film and the aerodynamics of the gas-phase peroxide. In order to reduce the occupied volume of the trapping module, the spiral diameter of the fifth spiral tube can be set to be in the range of 15-20 mm. When the spiral diameter is too large, the absorption liquid and the gas-phase peroxide sample need more power to pass through the spiral tube, which will increase the use cost of the device.

[0049] According to a preferred embodiment of the single-layer spiral trapping trap of the present application, the inner diameter of the fifth spiral tube can be set to 2.2 mm, and the spiral diameter can be set to 20 mm, so that the number of turns of the spiral tube is 15. The material of the fifth spiral tube is quartz glass, so that the resistance in the tube is moderate, and the absorption liquid forms a stable and thin liquid film on the inner wall of the tube by liquid tension, thereby increasing the gas-liquid absorption interface.

[0050] In the present application, other components can also be configured for the single-layer spiral trapping trap to help the single-layer spiral trapping trap obtain atmospheric samples and further process the absorption liquid samples obtained by the single-layer spiral trapping trap. The single-layer spiral trapping trap according to the embodiments of the present application can also include one or more of an absorption liquid pump, a liquid flow controller, a gas three-way valve, or a gas-liquid separation unit used in cooperation.

[0051] In some possible embodiments, the upper end of the single-layer spiral trapping trap can be connected to the gas three-way valve and the absorption liquid pump through independent pipelines, respectively. It can be understood that, in actual applications, in order to perform baseline and / or standard substance measurement on the device, the gas three-way valve can be connected to the single-layer spiral trapping trap to control switching between a sample gas collection mode for collecting atmospheric samples and a zero gas collection mode for collecting zero gas samples. In the zero gas collection mode, the zero gas sample enters the single-layer spiral trapping trap through the gas three-way valve to perform baseline zero-point measurement by the mixed double-layer spiral reaction chamber and any configurable fluorescence detection component. Specifically, after the zero gas sample is introduced, the single channel of the single-layer spiral trapping trap, the double channels of the mixed double-layer spiral reaction chamber, and / or the corresponding fluorescence detection component can be set to be consistent with the time sequence and program control in the sample gas collection mode, and the reaction consistency in the double channels when each device is used in combination can be obtained by zero-point and / or standard substance measurement on the zero gas sample. In addition, the baseline of the enzymolysis and fluorescence reaction of the mixed double-layer spiral reaction chamber can be corrected by calibration standard curve drawing and the like, so as to further improve the accuracy of hydrogen peroxide measurement by using the single-layer spiral trapping trap, the mixed double-layer spiral reaction chamber, and the corresponding components.

[0052] It should be noted that the flow rate and flow velocity of the absorption liquid need to be further balanced according to the size of the single-layer spiral trapping trap to ensure that the absorption liquid film can form a good coverage and distribution on the inner wall of the spiral tube. If the flow rate is too large, the liquid film can be too thick or broken; if the flow rate is too small or the flow velocity is too low, the liquid film can be incomplete or unevenly distributed. Therefore, the absorption liquid pump can be further configured with a liquid flow meter to accurately control the flow of the absorption liquid and continuously pump the absorption liquid into the single-layer spiral trapping trap, so as to form a stable absorption liquid film on the inner wall of the fifth spiral tube.

[0053] The absorption liquid sample obtained by the single-layer spiral trapping trap is usually transported to the reaction unit together with other gas-phase components in the atmospheric sample, so in order to avoid gas interference, the lower end of the single-layer spiral trapping trap can be first connected to a gas-liquid separation unit through a pipeline, and the trapping liquid sample and the gas-phase components not containing peroxide are transported to the gas-liquid separation unit for gas-liquid separation, and after classification, the trapping liquid sample is divided into two parts and transported to the double channels of the reaction module through the pipeline.

[0054] In some possible embodiments, the absorption liquid containing peroxide is continuously entrained by the rapidly flowing atmosphere continuously introduced by the gas three-way valve to move to the lower end of the single-layer spiral trapping trap, and the gas-liquid separation unit includes a gas-liquid separation chamber, a safety bottle, a filter membrane, a gas flow controller, a gas pump, and a bubble removal device; the absorption liquid exits the spiral pipe from the lower end and passes through the gas-liquid separation chamber, the absorption liquid sample is extracted from the bottom of the gas-liquid separation chamber by a propulsion assembly such as a peristaltic pump under the action of gravity and enters the bubble removal device, and the remaining atmosphere is discharged in turn after passing through the safety bottle, the filter membrane, the flow controller, and the gas pump under the action of the gas pump, and the discharge rate of these gases can be controlled. The absorption liquid sample is removed from the bubble removal device due to the incomplete dissolution of bubbles in the spiral pipeline during gas-liquid separation, and is further uniformly divided into A and B two ways by the bubble removal device, and is transported to the subsequent double channels such as the first channel and the second channel for reaction under the action of the propulsion assembly such as the peristaltic pump, that is, the first reaction chamber and the second reaction chamber of the mixed double-layer spiral reaction chamber according to the embodiments of the present application.

[0055] At present, the refrigeration of the trapping trap and the heating of the reaction chamber are basically designed based on the technical idea of attaching heating / cooling additional insulation cotton to the inner wall of the aluminum shell. This heating / cooling method transmits temperature to the pipeline through the heating / cooling components of the inner wall, which cannot guarantee the uniform and constant temperature of the pipeline up and down, and generally wraps the pipeline, which cannot observe the fluid state in the pipeline in real time. In addition, this heating / cooling method is generally more suitable for metal pipelines, and the temperature transfer efficiency of glass materials with higher specific heat capacity is poor. However, the trapping, transportation and reaction of hydrogen peroxide substances generally use glass material pipelines, which can maintain uniform temperature distribution of the spiral pipeline and facilitate the operator to observe the fluid running state in the pipeline in real time.

[0056] Therefore, the application is directed to a single-layer spiral trapping trap maintained at low temperature, a cooling guide directly contacting the single-layer spiral trapping trap of quartz material that needs to be cooled. The cooling guide is attached to the fifth spiral tube, and one end of the cooling guide is cooled by a refrigeration component, such as a plurality of refrigeration pieces, to instantly transfer the required temperature to the single-layer spiral trapping trap, so as to ensure uniform cooling of the single-layer spiral trapping trap and avoid the reduction of trapping efficiency caused by uneven temperature. Similarly, for a mixed double-layer spiral reaction chamber maintained at high temperature, a heat guide directly contacting the mixed double-layer spiral quartz reaction chamber that needs to be heated is designed, and a plurality of heaters, such as heat blocks, are connected and respectively contact the upper end to the lower end of the mixed double-layer spiral quartz reaction chamber, so as to ensure uniform heating of the reaction chamber and avoid the insufficient reaction caused by uneven heating of the reaction chamber, which affects the detection signal strength.

[0057] Specifically, the single-layer spiral trapping trap can further include a plurality of refrigeration components and a plurality of cooling guides; wherein the plurality of refrigeration components are arranged at the lower end of the fifth spiral tube, and the plurality of cooling guides respectively extend from the plurality of refrigeration components along the central spiral axis of the fifth spiral tube to the upper end of the fifth spiral tube in the middle and / or outer edge of the fifth spiral tube, so as to keep the overall temperature of the fifth spiral tube constant. When the number of cooling guides extending along the central spiral axis of the fifth spiral tube to the upper end of the fifth spiral tube in the middle of the fifth spiral tube is not less than 2, the cooling guides extending along the central spiral axis of the fifth spiral tube to the upper end of the fifth spiral tube in the middle of the fifth spiral tube are uniformly distributed, to help the single-layer spiral trapping trap to be uniformly cooled.

[0058] For the single-layer spiral trapping trap, more cooling guides and refrigeration components usually bring faster and more stable cooling effect, but the cost of equipment use also increases; in some possible embodiments, the number of cooling guides and refrigeration components that can be arranged for the fifth spiral tube can be between 3-8, so that the cooling guide can quickly cool and avoid waste of refrigeration materials. For example, 4 cooling guides and corresponding refrigeration components can be uniformly arranged on the outer edge of the fifth spiral tube, and 1 cooling guide and refrigeration component can be arranged in the middle of the fifth spiral tube, so as to uniformly cool the fifth spiral tube, and the cooling speed can meet the required time for starting the equipment under most detection conditions; as shown in the accompanying drawings, one cooling guide is attached to the upper and lower edges of the fifth spiral tube, and one cooling guide is fixed in the middle of the fifth spiral tube, to minimize the cost of refrigeration. Figure 2

[0059] ​Similarly, the second reaction chamber of the hybrid double-layer spiral reaction chamber may also include multiple heaters and multiple heat-conducting pipes; multiple heaters are disposed at the lower end of the second double-layer spiral tube, and multiple heat-conducting pipes extend from the multiple heaters along the central spiral axis of the second double-layer spiral tube to the upper end of the second double-layer spiral tube in the middle and / or along the outer edge of the second double-layer spiral tube, so as to maintain the overall temperature of the second double-layer spiral tube constant; when the number of heat-conducting pipes extending from the middle of the second double-layer spiral tube to the upper end of the second double-layer spiral tube along the central spiral axis of the second double-layer spiral tube is not less than 2, the heat-conducting pipes extending from the middle of the second double-layer spiral tube to the upper end of the second double-layer spiral tube are uniformly distributed to help the second reaction chamber be heated uniformly.

[0060] In some possible implementations, the number of heat-conducting pipes and heaters provided for the second double-layer spiral tube can be between 3 and 8, enabling rapid heat transfer and avoiding waste of heating materials. For example, four heat-conducting pipes and corresponding heaters can be evenly arranged along the outer edge of the second double-layer spiral tube, such as in a heat-conducting tube. Alternatively, one heat-conducting pipe and heater can be placed in the middle of the second double-layer spiral tube, allowing for uniform heat transfer. The heat transfer speed can also meet the equipment start-up time requirements in most detection scenarios. Here, since the second double-layer spiral tube is located after the fifth spiral tube, its required heating start-up time can be more generous, thus requiring fewer heat-conducting pipes to ensure stable heating. Furthermore, as shown in the attached figure... Figure 1 As shown, only one heat-conducting pipe is attached to the upper and lower edges of the second double-layer spiral tube, and one heat-conducting pipe is fixed in the middle, so as to minimize the heating cost.

[0061] Based on the aforementioned single-layer spiral trap and hybrid double-layer spiral reaction chamber, this application provides a device for measuring atmospheric hydrogen peroxide concentration, comprising a trapping module, a reaction module, a detection module, and a calculation module, such as... Figure 3 As shown in the diagram, the trapping module is connected to the input pipe of the reaction module to draw in the test sample from the atmosphere and trap the peroxides in the test sample to obtain a trapping liquid sample containing the test sample. The trapping module divides the trapping liquid sample into sample A and sample B and delivers them to the reaction module respectively. In the reaction module, they are processed separately and then subjected to fluorescence reaction to obtain two fluorescent reaction liquid samples. The detection module is connected to the output pipe of the reaction module to receive the two fluorescent reaction liquid samples and detect the total peroxide concentration in the two fluorescent reaction liquid samples respectively. The calculation module calculates the hydrogen peroxide concentration in the test sample based on the total peroxide concentration in the two fluorescent reaction liquid samples.

[0062] In some possible embodiments, the trapping module comprises an absorbent liquid pump, a liquid flow controller, a gas three-way valve, the single-layer spiral trapping trap mentioned above, and a gas-liquid separation unit, wherein the upper end of the single-layer spiral trapping trap is respectively connected with the gas three-way valve and the absorbent liquid pump pipeline; the gas three-way valve introduces the detection sample and / or the zero gas sample into the single-layer spiral trapping trap; the absorbent liquid pump introduces the absorbent liquid into the single-layer spiral trapping trap and forms an absorbent liquid film on the inner wall of the fifth spiral pipe, so as to trap the peroxide in the detection sample and obtain a trapping liquid sample; the lower end of the single-layer spiral trapping trap is connected with the gas-liquid separation unit pipeline, the gas-liquid separation unit separates the trapping liquid sample and the residual gas, and divides the trapping liquid sample into sample A and sample B to be respectively transported to the reaction module.

[0063] In some possible embodiments, the reaction module comprises the mixed double-layer spiral reaction chamber mentioned above; the first spiral pipe obtains sample A and parallel liquid by the peristaltic pump respectively, and mixes sample A and parallel liquid to obtain mixed solution A; the second spiral pipe obtains sample B and reaction liquid by the peristaltic pump respectively, and mixes sample B and reaction liquid to obtain mixed solution B; the third spiral pipe obtains mixed solution A and derivative liquid from the lower end of the first spiral pipe by the peristaltic pump respectively, and mixes mixed solution A and derivative liquid to obtain fluorescent reaction liquid sample A; and the fourth spiral pipe obtains mixed solution B and derivative liquid from the lower end of the second spiral pipe by the peristaltic pump respectively, and mixes mixed solution B and derivative liquid to obtain fluorescent reaction liquid sample B.

[0064] In some possible embodiments, the detection module comprises a fluorescent detection chamber for detecting fluorescent reaction liquid sample A and a fluorescent detection chamber for detecting fluorescent reaction liquid sample B; the fluorescent detection chamber for detecting fluorescent reaction liquid sample A and the fluorescent detection chamber for detecting fluorescent reaction liquid sample B are respectively connected with the lower end of the third spiral pipe and the lower end of the fourth spiral pipe.

[0065] The atmospheric hydrogen peroxide concentration measuring device according to the embodiments of the present application can further comprise a control module electrically connected with one or more of the trapping module, the reaction module, the detection module and the calculation module, and used for electrically controlling one or more of the trapping module, the reaction module, the detection module and the calculation module. The control module can be exemplified by a single-chip microcomputer, a DSP, an FPGA, etc. In addition, it can be understood that, in order to ensure that the atmospheric hydrogen peroxide concentration measuring device according to the embodiments of the present application normally uses liquid contents such as absorbent liquid, liquid sample, reaction liquid and / or derivative liquid, liquid conveying components can be appropriately increased according to actual application conditions, so as to ensure the normal flow of the above-mentioned liquid contents in the measuring device, for example, a peristaltic pump, a magnetic drive pump or a syringe, etc.

[0066] The integrated capture reaction integrated atmospheric hydrogen peroxide concentration measuring device provided by the application maximizes the common part of the two capture reaction paths, increases the sensitivity of the device, reduces the number of parts used by the device and the volume, and improves the portability of the device. The application designs a single-layer spiral capture trap in the measuring device, inserts a cold guide pipe at multiple positions such as the upper end, the middle, and the lower end of the spiral pipe of the single-layer spiral capture trap, uses the cold guide pipe as a cold transmission component, connects a refrigeration component at the tail end of the cold guide pipe, rapidly transmits low temperature to the whole end of the cold guide pipe, uniformly cools the single-layer spiral capture trap in real time, maintains constant low temperature from the upstream to the downstream of the single-layer spiral capture trap, reduces the refrigeration volume, and avoids the influence of uneven low temperature on the capture efficiency.

[0067] In addition, the application designs the reaction chamber for double-channel detection in the same reaction unit, simplifies the gas path, reduces the volume, and uses one high-temperature device to maintain the mixed double-layer spiral reaction chambers of the two channels in a constant high-temperature state, ensures uniform heating, avoids insufficient reaction caused by uneven temperature of the mixed double-layer spiral reaction chamber, and affects the signal strength detected. The entire measuring device is small in size, compact in structure, and can be used for online continuous monitoring of hydrogen peroxide in various operation scenes.

[0068] Embodiment

[0069] The application generally and / or specifically describes the materials and test methods used in the test. The raw materials or instruments not marked with the manufacturer are conventional raw material products or instruments that can be obtained from the market.

[0070] Embodiment 1

[0071] The composition structure of the atmospheric hydrogen peroxide concentration measuring device is shown in Figure 3 The device is used for online monitoring of the hydrogen peroxide content in the environment air, and the specific implementation manner is as follows:

[0072] The absorption liquid is precisely controlled by the liquid flow controller 1 under the action of the first peristaltic pump 13, is stably and continuously conveyed into the single-layer spiral capture trap 23 of the single-layer low-temperature capture module 2, sufficiently wets the inner wall of the single-layer spiral capture trap 23, and forms an absorption liquid surface layer on the inner wall of the single-layer spiral capture trap 23. When the atmospheric sample is analyzed, the sample gas, that is, the atmospheric sample, enters the single-layer spiral capture trap 23 kept at a constant temperature under the suction of the air pump 7, and the gaseous peroxide is fully absorbed by the absorption liquid surface layer on the inner wall of the trap due to molecular diffusion.

[0073] The liquid phase sample after absorbing the peroxide in the atmospheric sample to be measured is continuously carried to the downstream of the single-layer spiral trapping tank 23 under the action of the air flowing rapidly in the atmospheric sample, and reaches the gas-liquid separation unit 3 under the action of the second peristaltic pump 14. In the gas-liquid separation unit 3, the liquid phase sample after absorbing the peroxide to be measured is extracted from the bottom by the third peristaltic pump 15 and enters the bubble removal device 8 under the action of gravity, and the air in the remaining atmospheric sample is sequentially discharged to the safety bottle 4, the filter membrane 5 and the gas flow controller 6 under the action of the air pump 7.

[0074] After the liquid phase sample after absorbing the substance to be measured removes the bubbles in the pipeline due to incomplete gas-liquid separation through the bubble removal device 8, it is uniformly divided into two paths A and B to form sample A and sample B, and enters the first channel and the second channel of the mixed double-layer spiral reaction chamber 9 of the reaction module respectively. The liquid phase sample first enters the first double-layer spiral pipe in the mixed double-layer spiral reaction chamber 9, and deionized water and catalase solution enter the first channel and the second channel under the action of the fourth peristaltic pump 16 and the fifth peristaltic pump 17 respectively, wherein the catalase solution in the second channel is mixed with the liquid phase sample in the second spiral pipe, and hydrogen peroxide is rapidly decomposed under the action of catalase. Therefore, the hydrogen peroxide in the liquid phase sample solution in the second channel is rapidly consumed, and the hydrogen peroxide in the liquid phase sample solution in the first channel is retained, and the solutions in the two channels then enter the second double-layer spiral pipes of the two channels.

[0075] At the same time, the derivative liquid also enters the second double-layer spiral pipe under the action of the sixth peristaltic pump 18 and performs a fluorescence reaction with the peroxide in the liquid phase sample solution at a constant temperature of 40°C, the derivative liquid in the first channel reacts with total peroxide, and the derivative liquid in the second channel reacts with the peroxide in the liquid phase sample solution after removing hydrogen peroxide. After the reaction, the liquid phase sample solution in the two channels generates a fluorescence sample downstream in the flow direction and simultaneously enters the subsequent detection module 10 for measurement of the fluorescence signal intensity. The difference between the fluorescence signal intensities of the first channel and the second channel determines the accurate content of hydrogen peroxide in the liquid phase sample solution in the second channel decomposed by catalase, and thus the concentration of hydrogen peroxide in the atmospheric sample can be obtained.

[0076] The single-layer spiral trapping trap 23 at low temperature and the mixed double-layer spiral reaction chamber 9 at high temperature start working when the device is turned on, and remain constant low / high temperature. The liquid flow controller 1, the single-layer spiral trapping trap 23, the gas flow controller 6, the gas pump 7, the mixed double-layer spiral reaction chamber 9, the detection modules 10 and 11, the gas three-way valve 12, and the first to sixth peristaltic pumps 13-18 are all controlled by the control module 19 in real time to realize time sequence control of the entire device and each component, providing a solution for real-time and continuous atmospheric hydrogen peroxide monitoring.

[0077] When performing baseline and standard substance measurement, the gas three-way valve 12 is switched to zero gas mode, and the absorption liquid, deionized water, catalase, and derivative liquid are sequentially introduced into the single-layer spiral trapping trap 23 at low temperature and the mixed double-layer spiral reaction chamber 9 at high temperature under the control of the peristaltic pumps, respectively, for absorption and reaction. The zero gas sample is introduced into the device through the gas three-way valve 12 for baseline zero point measurement, and the time sequence control process of the sampling step, reaction step, and detection step is consistent with the measurement steps for atmospheric samples, so that the zero point hydrogen peroxide content of the first and second channels can be obtained. In this way, the consistency of the reaction and detection baseline of the two channels can be confirmed, and the calibration standard curve can be drawn for accurate calibration of the device and improvement of the reaction parallelism of the two channels to improve the accuracy of atmospheric hydrogen peroxide monitoring.

[0078] Example 2

[0079] The trapping module 2 includes a single-layer spiral trapping trap 23 made of quartz glass for absorbing atmospheric hydrogen peroxide and peroxide, and related components for maintaining low temperature, including a refrigeration component 24, a cold pipe 21, and an additional heat sink 25. The front-end trapping is integrated, and a single-channel spiral trapping trap can meet the trapping requirements, as shown in Figure 2 and Figure 3 After testing, the single-layer spiral trapping trap has an inner diameter of 2.2 mm, a spiral diameter of 20 mm, and 15 winding turns, with moderate resistance in the trap. The absorption liquid forms a thin absorption liquid layer on the inner wall of the trap by liquid tension, which can increase the gas-liquid absorption interface with atmospheric samples.

[0080] At a certain low-temperature trapping temperature, the saturation vapor pressure of peroxide is reduced, which makes it easier to be captured by the absorption liquid, thereby improving the enrichment efficiency. In addition, it also reduces the volume influence of air on the liquid, making the subsequent peroxide concentration measurement more accurate. After testing, setting the trapping temperature to 5°C can ensure a trapping efficiency of 100%, and also maximizes the absorption liquid carried away by the excess gas flow.

[0081] Since the single-layer spiral trapping trap is designed as a multi-turn spiral structure, simple refrigeration components such as refrigeration fins cannot uniformly cool it, which can easily cause uneven temperature in the tube.

[0082] To achieve effective control of the constant low temperature of the single-layer spiral trapping trap and reduce the volume of the refrigeration-related components, considering the efficient and rapid heat conduction performance of the heat conduction pipe, three heat conduction pipes 21 are respectively fixed in parallel along the sample flow direction at the center axis and both sides of the single-layer spiral trapping trap 23, so that the three heat conduction pipes 21 as a whole are in full contact with each part of the single-layer spiral trapping trap 23. Among them, the heat conduction pipes 21 located at the center axis and one side can ensure that the temperature on one side of the single-layer spiral trapping trap 23 remains uniform, and the heat conduction pipes 21 located at the center axis and the other side can ensure that the temperature on the other side of the single-layer spiral trapping trap 23 remains uniform. The three heat conduction pipes 21 are connected with the semiconductor refrigerator 24 arranged downstream of the single-layer spiral trapping trap 23 to provide continuous refrigeration.

[0083] Therefore, through the joint action of the three heat conduction pipes 21, the uniformity and constancy of the temperature in the single-layer spiral trapping trap 23 are ensured, and a heat-conducting silicone grease layer is also used for close fixing at the connection end of the three heat conduction pipes 21 and the semiconductor refrigeration fin 24. The hot end of the semiconductor refrigeration fin 24 is connected with the copper pipe radiator 25 through the heat-conducting silicone grease layer, thereby ensuring the continuous and efficient operation of the refrigeration fin.

[0084] In addition, in order to monitor the actual temperature in the trap in real time, a patch-type temperature sensor 22 is used, which is attached to the outer wall of the single-layer spiral trapping trap 23 at the middle position of the sample flow direction. Since the single-layer spiral trapping trap 23 is centrally symmetric at this position, and the heat conduction performance of quartz glass is good, therefore, the temperature sensor arranged here can ensure that it monitors the actual average temperature in the single-layer spiral trapping trap 23. In this way, large errors in temperature monitoring are avoided, which can cause uneven temperature in the tube. Such a simple and efficient arrangement can monitor the trapping temperature in real time by electrically connecting the patch-type temperature sensor 22 with the control module 19, and stop running or adjust the temperature of the trapping module 2 when necessary, so as to ensure that the sampling process strictly follows the set temperature parameters, and maintains high trapping efficiency.

[0085] Example 3

[0086] The reaction module 9 includes a second double-layer spiral pipe for contacting and reacting the to-be-tested substance with the derivative reagent, i.e., the derivative liquid for fluorescence reaction, to generate a fluorescent substance, and related components for maintaining high temperature, such as Figure 1 and Figure 3The two channels need to be divided into two pipelines for reaction respectively in the reaction stage. In order to simplify the gas circuit and the device, two spiral pipes arranged alternately in upper and lower positions are set as the third channel and the fourth channel to form the second double-layer spiral pipe 29 as the reaction chamber. The two channels are arranged by overlapping structure to reduce the volume, that is, only occupy the area of one channel in the axial direction, and the length is obviously shortened. The residence time of the solution in the second double-layer spiral pipe will affect the degree of fluorescence derivatization reaction. After testing, the inner diameter of the two channels is 1.5 mm, the spiral diameter is 25 mm, the winding number is 15, and the material is quartz glass, which can ensure sufficient derivatization reaction.

[0087] The temperature in the second double-layer spiral pipe as the reaction chamber will affect the reaction rate and the fluorescence quantum yield of the fluorescent substance. In order to achieve the best reaction and fluorescence effect, the reaction chamber needs to be controlled at a certain temperature. After testing, 35℃ is selected as the reaction temperature of the reaction chamber. In order to simplify the related parts of high temperature control and ensure the uniformity and constancy of the temperature in the pipe, this time, the red copper heat pipe with high heat conductivity, long service life and low unit price is used as the heat pipe to contact and heat the glass pipe. Three heat pipes 26 are uniformly placed at the upstream, middle and downstream positions of the second double-layer spiral pipe. A heating block 27 with a heating power of 50W is placed at one end of the heat pipe 26, such as the rear end. The heat generated by the heating block 27 is quickly transferred to the heat pipe 26, and the heat is transferred to the pipe through the heat pipe 26 with large surface area. The upstream and middle heat pipes can ensure the uniform temperature of the upper half of the second double-layer spiral pipe, and the middle and downstream heat pipes can uniformly heat the lower half of the second double-layer spiral pipe to ensure the uniform temperature. The three heat pipes work together to ensure the uniformity and constancy of the temperature in the spiral pipe.

[0088] In addition, in order to monitor the actual temperature in the pipe in real time, a patch type temperature sensor 28 is used, which is attached to the middle position of the second double-layer spiral pipe. The symmetrical structure can ensure that the actual temperature in the pipe is monitored, avoiding temperature monitoring error leading to uneven temperature in the pipe. This setting is simple and efficient, and can ensure the uniformity and consistency of the temperature of the second double-layer spiral pipe, meet the reaction temperature and ensure the feasibility and comparability of the double-layer pipe. The following table shows the reaction temperature required time of the fluorescence reaction in the reaction chamber when different number of heat pipes are set:

[0089] Table 1 Reaction temperature start-up time of mixed double-layer spiral reaction chamber under different number of heat pipes

[0090] Number of heat pipes Heat transfer rate (°C / s) Time to reach 35°C (s) 2 7 5 3 11.7 3 5 23.3 1.5 8 35 1 12 50 0.7

[0091] It can be seen that the number of heat conduction pipes is positively correlated with the time required to reach the reaction temperature. The second reaction chamber of the double-layer spiral reaction chamber heated by 5 heat conduction pipes only needs 1.5s, which reduces the start-up delay time of the equipment and maximizes the use efficiency of the equipment. In this embodiment, the second channel is used to decompose hydrogen peroxide in the absorption liquid, and the first channel does not treat hydrogen peroxide in the absorption liquid. First, add catalase solution to the second spiral pipe in the second channel, test the fluorescence signal intensity of the mixed solution of the absorption liquid and the catalase solution, and take the average value after multiple tests. The results are shown in Table 2.

[0092] Table 2 Influence of different parameters of the second spiral pipe on the fluorescence detection effect of the standard hydrogen peroxide solution of the measuring device

[0093]

[0094]

[0095] As can be seen from the above, the hydrogen peroxide in the absorption liquid is completely decomposed when the length of the second spiral pipe reaches 60 cm. In order to minimize the occupied volume of the second spiral pipe, the number of spiral turns is set to 9. Increasing the number of turns will increase the volume of the equipment and the measurement time, reduce the reaction efficiency and increase the cost of device manufacturing. Compressing the pitch will reduce the turbulence intensity in the spiral pipe, making the mixed flow of the absorption liquid and the catalase solution in the pipe more stable, which causes part of the solution to be wrapped by low flow turbulence and unable to effectively contact the heated pipe wall; in addition, the pipe wall itself with less gap is also more difficult to be heated from the surrounding heat conduction pipes. Therefore, the length of the second spiral pipe is preferably 60 cm and the number of turns is 9.

[0096] After determining the number of turns under the optimal length, the size of the spiral pipe inner diameter was also simulated and tested, and it was found that the catalase decomposition efficiency reached a maximum when the inner diameter of the spiral pipe increased to 1.1 mm. This is because the inner surface of the second spiral pipe made of quartz glass has a large liquid film and a large contact area between the solutions, which is beneficial to the liquid-liquid reaction of hydrogen peroxide and catalase. Further increasing the inner diameter, it is found that the hydrogen peroxide detection sensitivity of the device is reduced, which is caused by the strong longitudinal diffusion of the solution in the second spiral pipe. In this way, after the length of the second spiral pipe is determined, the optimal number of turns (9) and the optimal inner diameter (1.1 mm) are obtained by controlling the variable, so that the volume of the second spiral pipe is minimized while ensuring the high decomposition efficiency of hydrogen peroxide in it, thereby effectively supporting the subsequent difference detection. It can be understood that the first spiral pipe can also be set to the same structure, and the first spiral pipe and the second spiral pipe can be replaced with each other.

[0097] On this basis, the parameters of the spiral pipe for subsequent fluorescence reaction are further set, multiple tests are performed and the average value is taken, and the test results are shown in the following table.

[0098] Table 3 Influence of different parameters of the third spiral tube on the fluorescence detection effect of the measuring device on the standard hydrogen peroxide solution

[0099]

[0100]

[0101] The length of the third spiral tube can reach 120 cm to ensure that the derivatization solution and the peroxide are fully reacted in the shortest time and reach the maximum detection fluorescence signal value, reduce the volume of the device and the delay time. Similarly, the preferred number of winding turns of the third spiral tube is 13 turns, and too high a number of winding turns can affect the sufficient heating of the two reaction solutions, and the pitch needs to be limited to increase the turbulence intensity and improve the heat transfer efficiency.

[0102] After determining the number of winding turns at the optimal length, the inner diameter of the spiral tube was also simulated and tested, and it was found that the reaction efficiency reached the maximum when the inner diameter of the spiral tube was increased to 1.5 mm, because the liquid film on the inner surface of the third spiral tube made of quartz glass was large, the contact area between the solutions was large, which was beneficial to the full liquid-liquid reaction of the derivatization solution and the peroxide. Further increasing the inner diameter, it was found that the sensitivity of the device for detecting peroxide was reduced. It was obtained that when the length of the third spiral tube was 120 cm, the further preferred number of winding turns of the third spiral tube was 13 turns, and the inner diameter was 1.5 mm. It can be understood that the fourth spiral tube can also be provided with the same structure, and the third spiral tube and the fourth spiral tube can be replaced with each other.

[0103] In this way, the preferred size configuration of the first channel and the second channel and the length / pitch ratio and the length / inner diameter ratio under the length of the minimum reaction length that can be used are obtained, so that the volume of the reaction chamber can be contracted to the minimum, while the delay time of the device is maximized to reduce, ensure the parallelism and efficiency of the reaction in the two channels, so that the measuring device for atmospheric hydrogen peroxide concentration provided by the present application has smaller cost and wider practical use range, so as to monitor the atmospheric hydrogen peroxide in real time.

Claims

1. A hybrid dual-spiral reaction chamber, characterized in that, The application relates to a reaction chamber for detecting the concentration of peroxide in a sample. The reaction chamber comprises a first reaction chamber and a second reaction chamber arranged in sequence in the sample injection direction, wherein the first reaction chamber comprises a first double-layered spiral pipe composed of a first spiral pipe and a second spiral pipe arranged in mutual winding, and the second reaction chamber comprises a second double-layered spiral pipe composed of a third spiral pipe and a fourth spiral pipe arranged in mutual winding. The first spiral pipe and the third spiral pipe are detachably connected to form a first channel for detecting the concentration of peroxide in a sample. The second spiral pipe and the fourth spiral pipe are detachably connected to form a second channel for detecting the concentration of peroxide in a sample. The second reaction chamber comprises a plurality of heaters and a plurality of heat-conducting pipes.

2. The hybrid dual-layer spiral reaction chamber of claim 1, wherein, The plurality of heaters are arranged at the lower end of the second double-layered spiral pipe, and the plurality of heat-conducting pipes respectively extend from the plurality of heaters along the central spiral axis of the second double-layered spiral pipe to the upper end of the second double-layered spiral pipe at the middle and / or outer edge of the second double-layered spiral pipe to keep the overall temperature of the second double-layered spiral pipe constant. When the number of heat-conducting pipes extending from the middle to the upper end of the second double-layered spiral pipe along the central spiral axis of the second double-layered spiral pipe is not less than 2, the heat-conducting pipes extending from the middle to the upper end of the second double-layered spiral pipe are uniformly distributed. The heaters keep the temperature of the second reaction chamber at 30-45 DEG C. The first spiral pipe and the second spiral pipe are made of quartz glass or polytetrafluoroethylene. The inner diameter of the first spiral pipe and the second spiral pipe is 1-1.2 mm.

3. The hybrid dual-layer spiral reaction chamber of claim 1, wherein, The length of the first spiral pipe and the second spiral pipe is 30-90 cm. The winding number of the first spiral pipe and the second spiral pipe is 6-10 turns. The spiral diameter of the first spiral pipe and the second spiral pipe after winding is 10-15 mm. The third spiral pipe and the fourth spiral pipe are made of quartz glass or polytetrafluoroethylene. The inner diameter of the third spiral pipe and the fourth spiral pipe is 1.2-1.5 mm. The length of the third spiral pipe and the fourth spiral pipe is 90-130 cm. The winding number of the third spiral pipe and the fourth spiral pipe is 10-15 turns. The spiral diameter of the third spiral pipe and the fourth spiral pipe after winding is 15-20 mm. The number of the plurality of heat-conducting pipes is 3-8. The material of the plurality of heat-conducting pipes is one or more than one of pure copper, brass, combined heat pipe or nichrome heating wire. The length of the heat-conducting pipe is 120-150 cm, and the width of the heat-conducting pipe is 1-3 mm.

4. The hybrid dual-layer spiral reaction chamber of claim 2, wherein, The second reaction chamber further comprises a patch type temperature sensor. The number of the plurality of heat-conducting pipes is 8. The application relates to a reaction chamber for detecting the concentration of peroxide in a sample. ​ ​ 5. The hybrid dual-layer spiral reaction chamber of claim 4, wherein, ​ ​ 6. A single-layer spiral trapping trap characterized in that, ​ a fifth spiral pipe, a plurality of refrigeration components arranged at a lower end of the fifth spiral pipe, and a plurality of cold pipes respectively extending from the plurality of refrigeration components along a central spiral axis of the fifth spiral pipe at a middle and / or an outer edge of the fifth spiral pipe to an upper end of the fifth spiral pipe to keep the overall temperature of the fifth spiral pipe constant; when the number of cold pipes extending along the central spiral axis of the fifth spiral pipe at the middle of the fifth spiral pipe to the upper end of the fifth spiral pipe is not less than 2, the cold pipes extending at the middle of the fifth spiral pipe to the upper end of the fifth spiral pipe are uniformly distributed; the refrigeration components make the temperature of the fifth spiral pipe 0-10℃.

7. The single-layer spiral trapping trap of claim 6, wherein, wherein, the inner diameter of the fifth spiral pipe is 1.8-2.2mm; the length of the fifth spiral pipe is 40-100cm; the number of spiral turns of the fifth spiral pipe is 10-16 turns; and the spiral diameter of the fifth spiral pipe is 15-20mm.

8. The single-layer spiral trapping trap of claim 6, wherein, wherein, the number of the plurality of cold pipes is 3-8; the material of the plurality of cold pipes is pure copper and / or brass; and the length of the cold pipe is 120-150cm, and the width of the cold pipe is 1-3mm; the single-layer spiral trapping trap further comprises a patch temperature sensor.

9. The single-layer spiral trapping trap of claim 8, wherein, wherein, the number of the plurality of cold pipes is 8.

10. A device for measuring atmospheric hydrogen peroxide concentration, characterized by, including: a trapping module, a reaction module, a detection module, and a calculation module; the trapping module is connected with the input end pipeline of the reaction module, used for inhaling a detection sample from the atmosphere, and trapping peroxide in the detection sample to obtain a trapping liquid sample containing the detection sample; the trapping module divides the trapping liquid sample into sample A and sample B and respectively delivers them to the reaction module, which respectively processes them and obtains two fluorescence reaction liquid samples through fluorescence reaction after processing; the detection module is connected with the output end pipeline of the reaction module, used for receiving the two fluorescence reaction liquid samples and respectively detecting the total concentration of peroxide in the two fluorescence reaction liquid samples; the calculation module calculates the concentration of hydrogen peroxide in the detection sample based on the total concentration of peroxide in the two fluorescence reaction liquid samples.

11. The device for measuring atmospheric hydrogen peroxide concentration according to claim 10, wherein wherein, the trapping module includes an absorption liquid pump, a liquid flow controller, a gas three-way valve, a single-layer spiral trapping trap as claimed in any one of claims 6-9, and a gas-liquid separation unit, wherein the upper end of the single-layer spiral trapping trap is respectively connected with the gas three-way valve and the absorption liquid pump pipeline; the gas three-way valve introduces the detection sample and / or zero gas sample into the single-layer spiral trapping trap; the absorption liquid pump introduces absorption liquid into the single-layer spiral trapping trap and forms an absorption liquid film on the inner wall of the fifth spiral pipe to trap peroxide in the detection sample and obtain a trapping liquid sample; the lower end of the single-layer spiral trapping trap is connected with the gas-liquid separation unit pipeline, and the gas-liquid separation unit separates the trapping liquid sample and the remaining gas, and divides the trapping liquid sample into sample A and sample B to be delivered to the reaction module respectively.

12. The device for measuring atmospheric hydrogen peroxide concentration according to claim 10, wherein wherein, The reaction module comprises the mixed double-layer spiral reaction chamber according to any one of claims 1-5; The first spiral pipe obtains the sample A and the parallel liquid respectively by a peristaltic pump and mixes the sample A and the parallel liquid to obtain a mixed solution A, and the second spiral pipe obtains the sample B and the reaction liquid respectively by a peristaltic pump and mixes the sample B and the reaction liquid to obtain a mixed solution B; The third spiral pipe obtains the mixed solution A and the derivative liquid from the lower end of the first spiral pipe respectively by a peristaltic pump and mixes the mixed solution A and the derivative liquid to obtain a fluorescent reaction liquid sample A; The fourth spiral pipe obtains the mixed solution B and the derivative liquid from the lower end of the second spiral pipe respectively by a peristaltic pump and mixes the mixed solution B and the derivative liquid to obtain a fluorescent reaction liquid sample B.

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