CN105115921A - Detection device for detecting gas concentration in water - Google Patents
Detection device for detecting gas concentration in water Download PDFInfo
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- CN105115921A CN105115921A CN201510568145.6A CN201510568145A CN105115921A CN 105115921 A CN105115921 A CN 105115921A CN 201510568145 A CN201510568145 A CN 201510568145A CN 105115921 A CN105115921 A CN 105115921A
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Abstract
The invention discloses a detection device for detecting gas concentration in water. A gas permeation tube and a cuvette are arranged outsides a pump valve cabin and a control cabin; pressure balance between the inside and the outside of the pump valve cabin is realized; the control cabinet is internally provided with a support, a microprocessor chip, a photovoltaic conversion and I/V conversion circuit, an A/D conversion chip, a pump valve control switching circuit, first and second LED light sources, first and second photodiodes and a semi-transparent and semi-reflection mirror; the pump valve cabin is internally provided with a micro-flow pump, a three-way valve and a two-way valve; and the semi-transparent and semi-reflection mirror is arranged at an inner crossed part of a cross-shaped channel of the support. Exciting light of the first and second LED light sources is divided into two paths through the semi-transparent and semi-reflection mirror; one path of exciting light is partially absorbed by detected gas in the cuvette and permeation balance liquid of a reagent to enter the first photodiode to form a measurement signal; and the other path of exciting light directly enters the second photodiode to form a reference signal, and the measurement signal and the reference signal are used for obtaining concentration of the detected gas.
Description
Technical field
The present invention relates to a kind of pick-up unit for detecting gas concentration in water.
Background technology
Detection for gases such as Oceanic Carbon Dioxide, methane, sulfuretted hydrogen is long-standing.As far back as the 1950's, the scientist of the states such as Japan, the U.S., Britain just starts to utilize the means such as gravimetric method and balance pressure application to measure the inorganic carbon content dissolved in seawater.Such as, traditional Oceanic Carbon Dioxide detection method mainly contains Coulomb equation, vapor-phase chromatography and infrared spectrophotometer.
Coulomb equation is detection method coulomb meter and patent electrolytic solution combined, and it utilizes chemical reagent titration to be dissolved in carbon dioxide quantity in coulomb pond.The method is proposed in 1985 first by people such as JohnsonK.M., its advantage take electricity as examination criteria, without the need to primary standard substance, therefore higher sensitivity can be reached, but its pre-service is complicated, and influence factor is many, and its interfering ion reaches tens kinds, simultaneously titration starting point and terminal wayward, easily cause comparatively big error; In addition, electrode used therein vulnerable to pollution is corroded, and cannot realize long-time measurement.
Vapor-phase chromatography refers to by the chromatography of gas as order phase, it is as follows for the principle measuring seawater carbon dioxide: utilize air ebullator, tested seawater sample is made to reach pressure equilibrium (in the state of the equilibrium with air on the sea level of getting, think equal with air of water sample), then the gas after balance is passed into gas chromatographic analysis, obtain chromatogram, eventually pass a series of analytical calculation, obtain the gas concentration lwevel of seawater.In recent years, along with the development of gas chromatography isolation technics and related discipline, the detection perform of gas chromatography has had large increase, can reach higher precision, but it belongs to sampling analysis method, normally carry out experimental determination after collecting sample, complex operation, easily bring secondary pollution, meanwhile, the method requires harsh to running environment, equipment is complicated, required sample size is large, and Measuring Time is long, cannot meet the requirement of on-line monitoring.
Summary of the invention
The object of the invention is all or part of defect overcoming prior art, a kind of pick-up unit for detecting gas concentration in water is provided.
For achieving the above object, the technical solution used in the present invention is: the present invention comprises gas permeation tube, colorimetric pool, reagent bag, waste fluid bag, the pump valve cabin of sealing and the control cabinet of resistance to hydrostatic pressure for detecting the pick-up unit of gas concentration in water; Described gas permeation tube and colorimetric pool are arranged at outside pump valve cabin and control cabinet; Described pump valve cabin offers pump valve compartment, and the sealing of this pump valve compartment balance film 57 covers and is full of silicone oil in pump valve cabin and makes to realize inside and outside pump valve cabin pressure equilibrium; Be provided with microprocessor chip, opto-electronic conversion and I/V change-over circuit, A/D conversion chip, pump valve gauge tap circuit, the first LED light source, the second LED light source, the first photodiode, the second photodiode, bearing and semi-transparent semi-reflecting lens in described control cabinet, the first LED light source is different with the centre wavelength of the exciting light of the second LED light source; Micro-flow pump, T-valve and two-way valve is provided with in pump valve cabin; Described opto-electronic conversion is electrically connected with described first photodiode, the second photodiode respectively with the input end of I/V change-over circuit, opto-electronic conversion is electrically connected with the input end of A/D conversion chip with the output terminal of I/V change-over circuit, the output terminal of A/D conversion chip is electrically connected with the input end of described microprocessor chip, and the input end of described pump valve gauge tap circuit, the first LED light source, the second LED light source are electrically connected with the output terminal of microprocessor chip respectively; Described T-valve, micro-flow pump, two-way valve are electrically connected with the output terminal of pump valve gauge tap circuit respectively; Described bearing is provided with " ten " font passage, described semi-transparent semi-reflecting lens is placed in the inside intersection of two sub-channels of described " ten " font passage, and the two ends port of a wherein sub-channels of described " ten " font passage is respectively equipped with described second LED light source, described second photodiode; The port being somebody's turn to do one end of another sub-channels of " ten " font passage is provided with described first LED light source, and the port of the other end of this subchannel is connected with one end of incident optical; The other end of described incident optical is connected with the incident optical joint of described colorimetric pool, and the transmission fibre-optical splice of described colorimetric pool is connected with described first photodiode by transmission optical fiber; The entrance of described colorimetric pool and the outlet of described gas permeation tube, the entrance of described gas permeation tube and the outlet of described micro-flow pump, the import of described micro-flow pump is communicated with the public endpiece of described T-valve, an entrance point of described T-valve is communicated with reagent bag, the outlet of described colorimetric pool is communicated with the entrance point of described two-way valve, and the endpiece of described two-way valve is communicated with described waste fluid bag.
Further, the present invention also comprises cleaning fluid bag, and described cleaning fluid bag is communicated with another entrance point of described T-valve.
Further, the present invention also comprises reagent cabin, and described reagent bag and/or waste fluid bag are placed in described reagent cabin.
Further, the present invention also comprises reagent cabin, in described reagent bag, cleaning fluid bag, waste fluid bag any one or appoint and to be severally placed in described reagent cabin.
Further, be also provided with pin-saving chip in control cabinet of the present invention, the input end of described pin-saving chip is electrically connected with the output terminal of described microprocessor chip.
Further, the output terminal of pin-saving chip of the present invention is connected with outside PC.
Further, microprocessor chip of the present invention is connected with outside PC.
Further, the angle of two sub-channels of semi-transparent semi-reflecting lens of the present invention and described " ten " font passage is 45 °.
Further, the exciting light of the first LED light source of the present invention and the second LED light source enters colorimetric pool and all can occur absorption maximum effect after being absorbed by the osmotic equilibrium liquid of the reagent in colorimetric pool and tested gas.
Further, tested gas of the present invention is carbon dioxide, and the centre wavelength of the exciting light of the first LED light source is 620nm, and the centre wavelength of the exciting light of the second LED light source is 430nm, and the reagent in reagent bag is BTB reagent.
Compared with prior art, the invention has the beneficial effects as follows: (1) the present invention is by doing in-situ study to the reagent of tested gas sensitization such as the carbon dioxide in water body, methane, sulfuretted hydrogen and the osmotic equilibrium liquid of tested gas in the light absorption effect of certain wavelength, realize carrying out original position and on-line monitoring to the concentration of the gases such as the carbon dioxide in water body, methane, sulfuretted hydrogen, overcome the monitoring problem that prior art cannot carry out gas concentration in water body under the extreme pressure conditions such as deep-sea.(2) pick-up unit of the present invention is by the rational deployment of pump, valve and pipeline, the sequential flowing that the osmotic equilibrium liquid realizing the different measuring cycle connects in the front and back of pipeline, and then realize monitoring continuously gas (as carbon dioxide, methane etc.) tested in water body, there is the advantages such as high pressure resistant, broad quantum, highly sensitive, simple to operate and testing cost be low, eliminate the shortcomings such as the secondary pollution of sample, sample frequency be limited, for the original position and on-line monitoring problem solving tested gas provides an effective approach.(3) the present invention can eliminate the error because flashing brings surely, though make pick-up unit of the present invention under water long-play also there is very high measuring accuracy.
Accompanying drawing explanation
Fig. 1 is that the present invention is for detecting the structural representation of the pick-up unit of gas concentration in water;
Fig. 2 is the structural representation of control module;
Fig. 3 is the connection diagram of pick-up unit optical detecting module of the present invention and control module;
Fig. 4 is the schematic diagram of the gas collecting module of pick-up unit of the present invention;
Fig. 5 is the schematic diagram of carbon dioxide in the gas permeation tube collection water body of pick-up unit of the present invention;
Fig. 6 is the structural representation of the lower cover in the pump valve cabin of pick-up unit of the present invention;
Fig. 7 is the system responses value of carbon dioxide and the corresponding relation curve of standard density of carbon dioxide gas that utilize pick-up unit examination criteria water sample of the present invention to obtain.
In figure, 1. underwater electrical connector, 2. control cabinet, the upper cover of 2a. control cabinet, the lower cover of 2b. control cabinet, 2c. control module, 2d. bearing, 2e. battery, 21.LED light source, 22.LED light source, 23. incident opticals, 23a. incident optical sealed pressing sleeve, 32. transmission optical fiber, 32a. transmission optical fiber sealed pressing sleeve, 24. first photodiodes, 25. second photodiodes, 26. semi-transparent semi-reflecting lens, 3. colorimetric pool, 3a. incident optical joint, 3b. transmission fibre-optical splice, 3c. colorimetric pool entrance, 3d. colorimetric pool exports, 3e.8 colorimetric pool fixed mount, 3f. colorimetric pool fixed mount, 35. exudate pipes, 35a. exudate seal of tube gland, 4. gas permeation tube, 4a. gas permeation tube entrance, 4b. gas permeation tube exports, 4c. copper mesh cover, 43. penetrating fluid pipes, 5. pump valve cabin, the upper cover in 5a. pump valve cabin, the lower cover in 5b. pump valve cabin, 5c. fixed bar, 5d. fixed bar, 5e. watertight connecting line, 51. T-valve, 52. micro-flow pumps, 53. two-way valves, 54. feed tubes, 54a. feed tube sealed pressing sleeve, 55. pump valve compartment, 56. balance film glands, 57. balance films, 6. reagent cabin, the lower cover in 6b. reagent cabin, 61. reagent bags, 61a. reagent connecting pipe, 61b. reagent connecting pipe sealed pressing sleeve, 62. cleaning fluid bags, 62a. cleans connecting pipe, 62b. cleans connecting pipe sealed pressing sleeve, 63. waste fluid bags, 63a. waste liquid connecting pipe, 63b. waste liquid connecting pipe sealed pressing sleeve.
Embodiment
Below in conjunction with accompanying drawing, the present invention is further illustrated.
As shown in Figure 1, as one embodiment of the present invention, pick-up unit of the present invention comprises control cabinet 2, colorimetric pool 3, gas permeation tube 4, pump valve cabin 5 and reagent cabin 6.
As shown in Figure 1, through hole can be provided with at the center of the upper cover 2a of control cabinet 2, the underwater electrical connector 1 of 6 cores is installed in this through hole; Be fixedly connected with fixed bar 5d by fixed bar 5c between the lower cover 2b of the control cabinet 2 and upper cover 5a in pump valve cabin 5; Reagent cabin 6 is fixedly installed togather with the lower cover 5b in pump valve cabin 5; Gas permeation tube 4 and colorimetric pool 3 are arranged at the outside of control cabinet 2.Wherein, colorimetric pool 3 is fixedly installed togather with the lower cover 2b of control cabinet 2.Preferably, the present invention uses copper mesh cover 4c to wrap gas permeation tube 4, and, be fixedly connected with the upper cover 5a in pump valve cabin 5 by copper mesh cover 4c and gas permeation tube 4 and pump valve cabin 5 are fixedly installed togather.When using pick-up unit of the present invention, colorimetric pool 3 directly contacts with water body with gas permeation tube 4.As shown in Figure 5, copper mesh cover 4c water-permeable and air permeable, can avoid gas permeation tube 4 to be affected the osmotic efficiency of gas by biological attachment.Gas permeation tube 4 only allows gas penetrate through and do not allow Liquid Penetrant to pass through tube wall.To utilize bromothymol blue reagent (BromothymolBlue, being called for short BTB reagent) concentration that detects the carbon dioxide in water body is example, Liquid Penetrant is not allowed because gas permeation tube 4 allows gas to permeate, therefore, in the process that BTB reagent stops in gas permeation tube 4, carbon dioxide gas cognition in water body penetrates into gas permeation tube 4 and changes with BTB reagent reacting generation color in gas permeation tube 4, finally reaches osmotic equilibrium; Then, osmotic equilibrium liquid enters in colorimetric pool 3 through penetrating fluid pipe 43, in colorimetric pool 3, complete optical detection, obtains corresponding metrical information.
In the embodiment shown in Fig. 1, pick-up unit of the present invention is rendered as cylindrical shape in overall appearance, compact conformation, and can reduce the weight of whole pick-up unit, and make its aerial weight be about 5kg, weight is about 1kg under water.Control cabinet 2 of the present invention, pump valve cabin 5, reagent cabin 6 can adopt pressure-resistant material (as PEEK, POM etc.) to be processed into.The thickness of the tubular shell of control cabinet 2, upper cover 2a, lower cover 2b is about 10mm respectively, and the internal diameter of tubular shell is about.The two ends of the tubular shell of control cabinet 2 are sealed by screw and O RunddichtringO with upper cover 2a, lower cover 2b respectively and are fixedly installed togather.Control cabinet 2 can tolerate the hydrostatic force being not less than 3000m.For the watertightness performance making pick-up unit of the present invention reach 2000m under water, as shown in Figure 1, control module 2c and optical detecting module can be placed in the control cabinet 2 of resistance to hydrostatic pressure.
As shown in figures 1 and 3, optical detecting module mainly comprises bearing 2d, semi-transparent semi-reflecting lens 26, first LED light source 21, second LED light source 22, first photodiode 24, second photodiode 25, incident optical 23 and transmission optical fiber 32, wherein, bearing 2d is fixedly mounted on the lower cover 2b of control cabinet 2, and semi-transparent semi-reflecting lens 26, first LED light source 21, second LED light source 22, first photodiode 24 and the second photodiode 25 are fixedly installed on bearing 2d.Bearing 2d is provided with " ten " font passage, the port being somebody's turn to do the two ends of a sub-channels of " ten " font passage is installed with the second LED light source 22 and the second photodiode 25 respectively, the port of one end of another sub-channels is installed with the first LED light source 21, and the other end port of this subchannel is connected with one end of incident optical 23; The other end of incident optical 23 is connected with the incident optical joint of colorimetric pool 3, and the transmission fibre-optical splice of colorimetric pool 3 is connected with the first photodiode 24 by transmission optical fiber 32.For preventing outside body of water (as seawater) from infiltrating in control cabinet 2, as shown in Figure 1, when incident optical 23 passes the lower cover 2b of control cabinet, strictly seal with incident optical sealed pressing sleeve 23a; When transmission optical fiber 32 passes the lower cover 2b of control cabinet, strictly seal with transmission optical fiber sealed pressing sleeve 32a.In the inside intersection of two sub-channels, semi-transparent semi-reflecting lens 26 is installed.The angle of semi-transparent semi-reflecting lens 26 and two sub-channels is respectively 45° angle, make exciting light from the second LED light source 22 when through semi-transparent semi-reflecting lens 26, about have half light transmission semi-transparent semi-reflecting lens 26 and received as contrast signal by the second photodiode 25, second half light is entered incident optical 23 as optical signal transmissive by semi-transparent semi-reflecting lens 26 reflection; Similarly, the exciting light from the first LED light source 21 about has half to be reflected by semi-transparent semi-reflecting lens 26 and is received as contrast signal by the second photodiode 25, and second half light transmission is entered incident optical 23 as optical signal transmissive by semi-transparent semi-reflecting lens 26.Two-way optical signal transmissive transfers to colorimetric pool 3 through incident optical 23, when colorimetric pool 3, be delivered to the first photodiode 24 via transmission optical fiber 32 again after being absorbed a part by the osmotic equilibrium liquid of the reagent in colorimetric pool 3 and tested gas, received by the first photodiode 24 and produce measuring-signal.
As shown in Figure 2, control module 2c can comprise microprocessor chip, opto-electronic conversion and I/V change-over circuit, A/D conversion chip, pump valve gauge tap circuit and pin-saving chip.Whole control module 2c accessible site is that one piece of pcb board is fixedly mounted on the upper cover 2a of control cabinet 2.Wherein, opto-electronic conversion is electrically connected with the first photodiode 24, second photodiode 25 respectively with the input end of I/V change-over circuit, opto-electronic conversion is electrically connected with the input end of A/D conversion chip with the output terminal of I/V change-over circuit, the input end of microprocessor chip is electrically connected with the output terminal of A/D conversion chip, and the input end of pump valve gauge tap circuit, the input end of pin-saving chip, the first LED light source 21, second LED light source 22 are electrically connected with the output terminal of microprocessor chip respectively; In addition, as shown in Figure 1, Figure 2 and Figure 4, the T-valve 51 in pump valve cabin 5, micro-flow pump 52, two-way valve 53 are electrically connected with the output terminal of pump valve gauge tap circuit respectively by watertight connecting line 5e.
Battery 2e can be installed on control module 2c, be undertaken self-powered to make pick-up unit of the present invention by internal cell 2e.Pick-up unit of the present invention is also connected with external powering device with underwater cable by underwater electrical connector 1, thus is powered by outside.
As shown in Figure 1, reagent bag 61, cleaning fluid bag 62 and waste fluid bag 63 are placed in reagent cabin 6, the flexible packaging of all available Fresco Bag of reagent bag 61, cleaning fluid bag 62 and waste fluid bag 63.Reagent cabin 6 is provided with opening, and outside water body can enter in reagent cabin 6 by this opening, in addition, also can change reagent bag 61, cleaning fluid bag 62 and waste fluid bag 63 and liquid wherein easily via this opening.As another embodiment of the invention, reagent cabin 6 can not being established, when measuring, reagent bag 61, cleaning fluid bag 62 and waste fluid bag 63 being directly placed in water body.
As shown in Figure 1, pump valve cabin 5 is made up of high voltage bearing housing and the upper cover 5a in pump valve cabin and the lower cover 5b in pump valve cabin.The upper cover 5a in pump valve cabin is fixedly connected with fixed bar 5d by fixed bar 5c with the lower cover 2b of control cabinet.As shown in Figure 6, the lower cover 5b in pump valve cabin 5 there is pump valve compartment 55, this hole is the circular hole of diameter, pump valve compartment 55 uses balance film 57(as fluid-tight rubber or plastic sheeting) cover and use balance film gland 56 and CARBURIZING FURNACE FOR STAINLESS FASTENER fixing seal, make the inside in pump valve cabin 5 be the environment sealed thus, be used in the water body of 0-2000m and detect gas concentration.Owing to being full of silicone oil with low viscosity in pump valve cabin 5, and balance film 57 has elasticity, when pick-up unit of the present invention is placed in deep water, the hydrostatic force of outside body of water makes balance film 57 elasticity cave in, make the silicone oil of inside, pump valve cabin 5 produce identical hydrostatic force, thus the pressure maintained in the pump of inside, pump valve cabin 5, valve and pipeline thereof and the pressure in gas permeation tube 4, colorimetric pool 3, reagent bag 61, cleaning fluid bag 62 and pipeline thereof completely the same and can normally work.Due to the internal and external pressure balance design in the withstand voltage design of control cabinet 2 and pump valve cabin, reagent cabin, whole pick-up unit of the present invention can be placed in the deep water within 2000m by cloth, ensure pump, valve normally can work under different high hydrostatic pressures.
T-valve 51, micro-flow pump 52 and two-way valve 53 are placed in airtight pump valve cabin 5.Wherein, T-valve 51, micro-flow pump 52 and two-way valve 53 are fixedly mounted on the lower cover 5b in pump valve cabin 5.Reagent bag 61, cleaning fluid bag 62 is respectively by the reagent connecting pipe 61a of lower cover 5b running through pump valve cabin 5, cleaning fluid bag connecting pipe 62a is communicated with two entrance points of T-valve 51, the public endpiece of T-valve 51 and the inlet communication of micro-flow pump 52, the outlet of micro-flow pump 52 is communicated with the gas permeation tube entrance 4a of gas permeation tube 4 by feed tube 54, the gas permeation tube outlet 4b of gas permeation tube 4 is communicated with colorimetric pool entrance 3c by penetrating fluid pipe 43, colorimetric pool outlet 3d is communicated with by the entrance point of exudate pipe 35 with two-way valve 53, the endpiece of two-way valve 53 is communicated with waste fluid bag 63 by waste liquid connecting pipe 63a.When reagent connecting pipe 61a, cleaning connecting pipe 62a, waste liquid connecting pipe 63a pass the lower cover 5b in pump valve cabin, strictly seal with reagent connecting pipe sealed pressing sleeve 61b, cleaning fluid connecting pipe sealed pressing sleeve 62b, waste liquid connecting pipe sealed pressing sleeve 63b respectively.Feed tube 54 and exudate pipe 35, when the upper cover 5a through pump valve cabin, strictly seal with feed tube sealed pressing sleeve 54a and exudate sealed pressing sleeve 35a respectively.In the present invention, T-valve 51 and micro-flow pump 52 can select three-way solenoid valve (LFRA2430110H) and the micro-flow pump (LPLA1211050L) of LEE company of the U.S. respectively.The liquid capacity that the every action of micro-flow pump (LPLA1211050L) is once extracted is 50 μ L.
When using pick-up unit of the present invention to measure, the input end of microprocessor chip can be electrically connected by underwater electrical connector 1 and underwater cable with PC waterborne, thus by PC waterborne to microprocessor chip sending controling instruction, by microprocessor chip, steering order is transmitted to control pump valve gauge tap circuit, the first LED light source 21 and the second LED light source 22 again, thus makes microprocessor chip control conducting and the closedown of pump valve gauge tap circuit, the first LED light source 21 and the second LED light source 22 according to the instruction of PC.As another embodiment of the invention, also directly can send steering order by microprocessor chip self, the conducting of control pump valve gauge tap circuit, the first LED light source 21, second LED light source 22 and closedown.
Microprocessor chip controls micro-flow pump 52, T-valve 51, the conducting of two-way valve 53 and closedown by controlling pump valve gauge tap circuit, thus select to open T-valve 51 and cleaning fluid bag 62 or and reagent bag 61 between pipeline, and extract cleaning fluid or reagent under the effect of micro-flow pump 52.When selecting extraction reagent carries out gas concentration detection, the cleaning fluid import of T-valve 51 is closed, the reagent entry port of T-valve 51 is opened, reagent in reagent bag 61 enters T-valve 51 through reagent connecting pipe 61a from the reagent entry port end of T-valve 51, micro-flow pump 52 is entered again from the public endpiece of T-valve 51, then gas permeation tube 4 is entered through feed tube 54 by gas permeation tube entrance 4a, reagent in gas permeation tube 4 with permeated after the tested gas (as carbon dioxide) of coming in mixes and reach osmotic equilibrium by water body, enter colorimetric pool 3 by gas permeation tube outlet 4b through penetrating fluid pipe 43 and carry out gas concentration detection, waste liquid after detection exports 3d by colorimetric pool and to be transported to two-way valve 53 in pump valve cabin 5 through vent pipe 35, to be entered through waste liquid connecting pipe 63b by the outlet of two-way valve 53 again in the waste fluid bag 63 in reagent cabin.Thus, define by reagent bag 61, to the closing pipe line that waste fluid bag 63 terminates.Because two-way valve 53 is positioned at the terminal of fluid path, when two-way valve 53 is in closed condition, can ensure to avoid waste liquid to pour in down a chimney and microorganism etc. pollutes pipeline.
Microprocessor chip can select the MSP430F2XX series microprocessor chip of TI company.The PWM ripple that microprocessor chip produces certain frequency drives the first LED light source 21 and the second LED light source 22 to produce the exciting light with different wave length respectively.Such as, the first LED light source 21 produces the exciting light that centre wavelength is 620nm, and the second LED light source 22 produces the exciting light that centre wavelength is 430nm.Two bundle exciting lights are divided into two-way after semi-transparent semi-reflecting lens 26, and wherein a road directly enters the second photodiode 25 and obtains contrast signal; Another road is finally delivered to the first photodiode 24 and obtains measuring-signal after absorbing via the osmotic equilibrium liquid of the reagent in colorimetric pool 3 and tested gas.Measuring-signal received by first photodiode 24, second photodiode 25 and contrast signal are converted into direct current signal through opto-electronic conversion and I/V change-over circuit, convert digital signal to through 24 A/D conversion chips again and be sent to microprocessor chip, digital signal information is transferred in pin-saving chip (as FLASH memory) and preserves by microprocessor chip.The output terminal of superimpose data storage chip is connected with the PC of the water surface with underwater cable by underwater electrical connector 1, when needed the information that pin-saving chip stores can be uploaded to PC; Certainly, if need to make Real-Time Monitoring to the gas concentration in water body, the information that the PC of the water surface can also store in Real-time Obtaining pin-saving chip.As another embodiment of the invention, usage data storage chip can also not realize the real time on-line monitoring to the gas concentration in water body, that is: when measuring, the output terminal of microprocessor chip directly can be electrically connected with the PC of the water surface by underwater electrical connector 1 and underwater cable, thus the measurement data in microprocessor chip is directly uploaded to PC in real time.
The midband that the PWM ripple produced by microprocessor chip drives the first LED light source 21 and the second LED light source 22 to produce about 2kHz exchanges light, realizes the detection of feeble signal.The low power consumption characteristic of LED light source, has that luminosity is stable, efficiency advantages of higher.A/D conversion chip can use the ADS1246 chip of TI company.ADS1246 chip is 24 high-precision A/D, and the highest output frequency reaches 2KSPS, and it is communicated with microprocessor chip by spi bus, and the output frequency arranging A/D is 5SPS, and bipolarity is sampled.Pin-saving chip can use FLASH memory AD45DB081B.Microprocessor chip, by spi bus, is preserved in digital data transmission to FLASH memory AD45DB081B.
As shown in Figure 4, gas collecting module mainly comprises: microprocessor chip, pump valve gauge tap circuit, reagent bag 61, cleaning fluid bag 62, T-valve 51, micro-flow pump 52, two-way valve 53, gas permeation tube 4, colorimetric pool 3, waste fluid bag 63 and corresponding connecting line.For completing the in-situ acquisition of gas concentration lwevel information in water, the microprocessor chip in control module 2c opens T-valve 51 and micro-flow pump 52 by controlling pump valve gauge tap circuit, thus extracts the BTB reagent in reagent bag 61.BTB reagent is input in gas permeation tube 4 by micro-flow pump 52, BTB reagent stay for some time in gas permeation tube 4 and with permeate the carbon dioxide of coming in from outside body of water and be combined and reach osmotic equilibrium, then enter in colorimetric pool 3 together.The light absorption signal of the osmotic equilibrium liquid in colorimetric pool 3 is gathered by the optical signal transmissive from the first LED light source 21 and the second LED light source 22 entering colorimetric pool 3.When the tested gas in water be carbon dioxide, the centre wavelength of the exciting light of the first LED light source 21 is 620nm, the centre wavelength of the exciting light of the second LED light source 22 is 430nm, reagent in reagent bag is BTB reagent time, the exciting light of the first LED light source and the second LED light source enters colorimetric pool 3 and all occurs absorption maximum effect after being absorbed by the osmotic equilibrium liquid of the BTB reagent in colorimetric pool 3 and carbon dioxide.
The using method of pick-up unit of the present invention is described with specific embodiment below:
(1) first, can clean it before pick-up unit of the present invention is put into water, preliminary examination.
The input end of microprocessor chip is connected with outer PC with cable by underwater electrical connector, and the output terminal of pin-saving chip is connected with PC with cable by underwater electrical connector.There is provided 12V power supply by outside to pick-up unit by underwater electrical connector or enable internal cell 2e.System initialization reading system parameter, completion system is started shooting.Microprocessor chip receives the clear instruction of outer PC, micro-flow pump 52 and two-way valve 53 is opened by pump valve gauge tap circuit, and close the reagent entry port of T-valve 51 and open its cleaning fluid import, thus select the cleaning fluid in cleaning fluid bag 62 to pump into T-valve 51, after successively via micro-flow pump 52, gas permeation tube 4, colorimetric pool, two-way valve 53, waste fluid bag 63, thus clean whole pipeline.After having cleaned, microprocessor chip receives the measurement instruction of outer PC, open micro-flow pump 52 and two-way valve 53 by pump valve gauge tap circuit, and close the cleaning fluid import of T-valve 51 and open its reagent entry port, thus selecting extraction reagent enters above-mentioned pipeline.The spectrophotometric value of the reagent in direct reading colorimetric pool 3.For BTB reagent, in fluid path and colorimetric pool in bubble-free, inclusion-free, the normal situation of light path, the ratio of the spectrophotometric value of BTB reagent under the effect of the first LED light source 21 and the second LED light source 22 is less than 0.8, can substantially get rid of thus to exist to cause the situation of measuring error (having bubble, impurity etc. to affect the situation of accuracy of measurement in such as pipeline).So far preliminary examination is completed.
(2) after, the input end of microprocessor chip is connected with water surface PC with cable in water by underwater electrical connector, and the output terminal of pin-saving chip is connected with water surface PC with cable in water by underwater electrical connector.After the predetermined depth that pick-up unit of the present invention puts into water body, water surface PC sends measurement instruction to microcontroller chip, enters automatic measuring phases.
As one embodiment of the present of invention, the internal capacity of colorimetric pool 3 is 70 μ L, and the length of gas permeation tube 4 is 20cm, the osmotic equilibrium liquid about 100 μ L stopped in gas permeation tube 4, the length of penetrating fluid pipe 43 is about 15cm, the pipe inner capacities about 165 μ L of penetrating fluid pipe 43.Microcontroller chip in control module 2c passes through conducting and the closing motion of pump valve gauge tap control circui T-valve 51, micro-flow pump 52 and two-way valve 53, further, the first LED light source 21 is controlled by microprocessor chip and the first LED light source 22 carries out exciting action.
When starting a new measuring period, microcontroller chip opens the reagent entry port of micro-flow pump 52, two-way valve 53 and T-valve 51 by controlling pump valve gauge tap circuit.Micro-flow pump 52 carries out the action that 5 times are extracted novel agent continuously, and each extraction reagent 50 μ L, amounts to 250 μ L 5 times.In the process of micro-flow pump 52 continuous drawing novel agent, novel agent also starts to carry to gas permeation tube 4, simultaneously, the liquid retained in the osmotic equilibrium liquid to be detected that a upper measuring period of retaining in gas permeation tube 4 is formed and penetrating fluid pipe 43 also starts to carry to colorimetric pool 3, and that retains in colorimetric pool 3 had detected complete osmotic equilibrium liquid (namely go up the osmotic equilibrium liquid of formation last measuring period) in a upper measuring period and then start to carry to waste fluid bag 63 direction.
It should be noted that, before the liquid retained in penetrating fluid pipe 43 starts to carry to colorimetric pool 3, liquid in penetrating fluid pipe 43 is the reagent without osmotic equilibrium extracted upper measuring period substantially, the reagent that the last measuring period simultaneously allowing the leading portion existence part of penetrating fluid pipe 43 not yet to enter colorimetric pool 3 is extracted and the osmotic equilibrium liquid of gas and the reagent without osmotic equilibrium.Because penetrating fluid pipe 43 is between colorimetric pool 3 and gas permeation tube 4, therefore, before the osmotic equilibrium liquid to be detected of a upper measuring period arrives colorimetric pool 3, the reagent without osmotic equilibrium that the former upper measuring period resided in penetrating fluid pipe 43 is extracted is in the process of flowing, leading to the pipeline of process and colorimetric pool 3 rinse and purify, the precision of the Concentration Testing of the osmotic equilibrium liquid to be detected that the Liquid Residue impact of the osmotic equilibrium liquid avoiding formed last measuring period is formed a upper measuring period.
When extracting release 5 times of micro-flow pump 52, micro-flow pump 52, two-way valve 53 and T-valve 51 are closed.Now, in gas permeation tube 4, the whole of stop are the novel agents (100 μ L) extracted this measuring period, are then full of the osmotic equilibrium liquid to be detected formed a measuring period in colorimetric pool 3.Simultaneously, microprocessor chip instruction first LED light source 21 light source and the second LED light source 22 produce exciting light, the two-way optical signal transmissive that the exciting light of the first LED light source 21 light source and the second LED light source 22 obtains after semi-transparent semi-reflecting lens 26 enters colorimetric pool 3 through incident optical 23, thus the osmotic equilibrium liquid to be detected of a upper measuring period in contrast colors pond 3 carries out optical detection, measurement data was stored to pin-saving chip simultaneously or was sent to PC and show and make further analyzing and processing.When the 100 μ L novel agents stopped in gas permeation tube 4 reach osmotic equilibrium, complete this measuring period.So microcontroller chip opens the reagent entry port end of micro-flow pump 52, two-way valve 53 and T-valve 51 by pump valve gauge tap circuit, enter next measuring period.Thus, the present invention realizes the continual measurement to gas concentration in water body.
It should be noted that, when completing this measuring period, what stop in gas permeation tube 4 is the reagent of this measuring period of extraction to be detected and the osmotic equilibrium liquid of gas, what stop in colorimetric pool 3 is detected complete osmotic equilibrium liquid (namely going up the osmotic equilibrium liquid of reagent and the gas extracted a measuring period) this measuring period, the reagent (without osmotic equilibrium) extracted this measuring period is stopped in feed tube 54, the reagent without osmotic equilibrium having extract this measuring period is then stopped in penetrating fluid pipe 43, and the reagent and the osmotic equilibrium liquid of gas and the reagent without osmotic equilibrium that extract last measuring period that part not yet enters colorimetric pool 3 may be there is at the leading portion of penetrating fluid pipe 43.
The detailed process that the osmotic equilibrium liquid to be detected that a upper measuring period within each measuring period in contrast colors pond 3 is formed carries out optical detection is as follows: the PWM ripple produced by microprocessor chip drives the first LED light source 21 and the second LED light source 22 to produce the exciting light of different wave length respectively, such as, first LED light source 21 produces the excitaton source that centre wavelength is 620nm, and the second LED light source 22 produces the exciting light that centre wavelength is 430nm.The exciting light that first LED light source 21 and the second LED light source 22 produce is divided into through Beam and a branch of reflected light separately by semi-transparent semi-reflecting lens 26, wherein, utilizing emitted light from the first LED light source 21 and the transmitted light from the second LED light source 22 are directly received by the second photodiode 25, thus corresponding generation two contrast signal (absorbance value) R21 and R22; From the transmitted light of the first LED light source 21 with enter colorimetric pool 3 from the reflected light of the second LED light source 22 via incident optical 23, through being received by the first photodiode 24 by transmission optical fiber 32 after being partially absorbed by osmotic equilibrium liquid in colorimetric pool 3, corresponding generation two measuring-signal (absorbance value) M21 and M22 thus.Measuring-signal (M21, M22) and contrast signal (R21, R22) are converted into direct current signal respectively through opto-electronic conversion and I/V change-over circuit, transform chip through 24 AD again and convert digital signal to, and then be transferred to microprocessor chip, by microprocessor chip, the signal value of digital signal M21, M22, R21, R22 and the temporal information etc. of correspondence are transferred to preservation in pin-saving chip (as FLASH memory).
When calculating the gas concentration lwevel in tested water body, outer PC reads the measuring-signal (M21, M22) of corresponding time point and the signal value of contrast signal (R21, R22) from FLASH memory or directly from microprocessor chip, deduct contrast signal value (absorbance value) by the measurement signal value (absorbance value) of corresponding LED light source and obtain osmotic equilibrium liquid light absorption value difference A1 and A2 under two light sources, i.e. A1=M21-R21, A2=M22-R22; By calculating the ratio A2/A1 of A2 and A1, the system responses value of tested gas concentration just can be obtained.The system responses value of aforementioned tested gas concentration showing of setting up in advance in the equation of system responses value and tested gas concentration corresponding relation, can be obtained the concentration value of the carbon dioxide of this Measuring Time point for people.Owing to can both be eliminated the error because flashing brings surely by the difference calculating the respective measurement signal value of two kinds of light sources and contrast signal value when measuring each time, though make pick-up unit of the present invention under water long-play also there is very high measuring accuracy.
It should be noted that, before use pick-up unit of the present invention detects the concentration of tested gas, apparatus of the present invention are first utilized to measure the system responses value of calibrating gas sample within the scope of 200-900ppm of several concentration known, thus the standard equation of corresponding relation between system responses value and gas concentration setting up that pick-up unit of the present invention obtains.Specifically, as shown in Figure 7, within the scope of 200-900ppm by the standard water sample concentration of known gas concentration lwevel as Y-axis, detecting to standard water sample the system responses value A2/A1 obtained with apparatus of the present invention measurement is X-axis, draws and obtains the typical curve that apparatus of the present invention detect gas concentration lwevel.From this typical curve, direct proportionality between tested gas concentration and system responses value.The linear fit related coefficient utilizing pick-up unit of the present invention to set up calibration curve reaches 0.9915, illustrates that pick-up unit of the present invention has higher reliability.According to this typical curve can obtain further utilizing pick-up unit of the present invention obtain the equation of corresponding relation between the system responses value of tested gas and tested gas concentration.
As one embodiment of the present invention, the computation process of the gas concentration lwevel in tested water body also can directly complete in microprocessor chip.Then, the result of calculation of tested gas concentration to be stored in pin-saving chip or the PC that is directly sent to the water surface by microprocessor chip shows in real time and reads by microprocessor chip.The result of calculation being stored in the tested gas concentration of pin-saving chip can send to PC when needed again, also PC can be sent in real time to carry out showing and reading by pin-saving chip.
It should be noted that, pick-up unit of the present invention, except can detecting the concentration of carbon dioxide in water body, can also be used for detecting the concentration of other gases (such as methane, sulfuretted hydrogen etc.) in water body.Those skilled in the art can utilize prior art knowledge, determine the centre wavelength of used reagent and the first LED light source matched and the second LED light source according to the concrete gas that will detect, its criterion all can occur that absorption maximum effect is advisable after to be the exciting light that enters the first LED light source in colorimetric pool 3 and the second LED light source absorbed by the osmotic equilibrium liquid of the tested gas in colorimetric pool and reagent.
Claims (10)
1. for detecting a pick-up unit for gas concentration in water, it is characterized in that: comprise gas permeation tube (4), colorimetric pool (3), reagent bag (61), waste fluid bag (63), the pump valve cabin (5) of sealing and the control cabinet (2) of resistance to hydrostatic pressure; Described gas permeation tube (4) and colorimetric pool (3) are arranged at pump valve cabin (5) and control cabinet (2) outward; Described pump valve cabin (5) offers pump valve compartment (55), and this pump valve compartment (55) seals with balance film 57 and covers and be full of silicone oil in pump valve cabin (5) and make to realize inside and outside pump valve cabin (5) pressure equilibrium; Be provided with microprocessor chip, opto-electronic conversion and I/V change-over circuit, A/D conversion chip, pump valve gauge tap circuit, the first LED light source (21), the second LED light source (22), the first photodiode (24), the second photodiode (25), bearing (2d) and semi-transparent semi-reflecting lens (26) in described control cabinet (2), the first LED light source (21) is different with the centre wavelength of the exciting light of the second LED light source (22); Micro-flow pump (52), T-valve (51) and two-way valve (53) is provided with in pump valve cabin (5); Described opto-electronic conversion is electrically connected with described first photodiode (24), the second photodiode (25) respectively with the input end of I/V change-over circuit, opto-electronic conversion is electrically connected with the input end of A/D conversion chip with the output terminal of I/V change-over circuit, the output terminal of A/D conversion chip is electrically connected with the input end of described microprocessor chip, and the input end of described pump valve gauge tap circuit, the first LED light source (21), the second LED light source (22) are electrically connected with the output terminal of microprocessor chip respectively; Described T-valve (51), micro-flow pump (52), two-way valve (53) are electrically connected with the output terminal of pump valve gauge tap circuit respectively; Described bearing (2d) is provided with " ten " font passage, described semi-transparent semi-reflecting lens (26) is placed in the inside intersection of two sub-channels of described " ten " font passage, and the two ends port of a wherein sub-channels of described " ten " font passage is respectively equipped with described second LED light source (22), described second photodiode (25); The port being somebody's turn to do one end of another sub-channels of " ten " font passage is provided with described first LED light source (21), and the port of the other end of this subchannel is connected with one end of incident optical (23); The other end of described incident optical (23) is connected with the incident optical joint of described colorimetric pool (3), and the transmission fibre-optical splice of described colorimetric pool (3) is connected with described first photodiode (24) by transmission optical fiber (32); The entrance of described colorimetric pool (3) and the outlet of described gas permeation tube (4), the entrance of described gas permeation tube (4) and the outlet of described micro-flow pump (52), the import of described micro-flow pump (52) is communicated with the public endpiece of described T-valve (51), an entrance point of described T-valve (51) is communicated with reagent bag, the outlet of described colorimetric pool (3) is communicated with the entrance point of described two-way valve (53), and the endpiece of described two-way valve (53) is communicated with described waste fluid bag.
2. the pick-up unit for detecting gas concentration in water according to claim 1, is characterized in that: also comprise cleaning fluid bag (62), and described cleaning fluid bag is communicated with another entrance point of described T-valve (51).
3. the pick-up unit for detecting gas concentration in water according to claim 1, is characterized in that: also comprise reagent cabin (6), and described reagent bag (61) and/or waste fluid bag (63) are placed in described reagent cabin.
4. the pick-up unit for detecting gas concentration in water according to claim 2, it is characterized in that: also comprise reagent cabin (6), in described reagent bag (61), cleaning fluid bag (62), waste fluid bag (63) any one or appoint and to be severally placed in described reagent cabin.
5. the pick-up unit for detecting gas concentration in water according to any one of claim 1 to 4, it is characterized in that: described control cabinet is also provided with pin-saving chip in (2), the input end of described pin-saving chip is electrically connected with the output terminal of described microprocessor chip.
6. the pick-up unit for detecting gas concentration in water according to claim 5, is characterized in that: the output terminal of described pin-saving chip is connected with outside PC.
7. the pick-up unit for detecting gas concentration in water according to any one of claim 1 to 6, is characterized in that: described microprocessor chip is connected with outside PC.
8. the pick-up unit for detecting gas concentration in water according to any one of claim 1 to 7, is characterized in that: described semi-transparent semi-reflecting lens (26) is 45 ° with the angle of two sub-channels of described " ten " font passage.
9. the pick-up unit for detecting gas concentration in water according to any one of claim 1 to 8, is characterized in that: the exciting light of described first LED light source and the second LED light source enters colorimetric pool (3) and all can occur absorption maximum effect after being absorbed by the osmotic equilibrium liquid of the reagent in colorimetric pool (3) and tested gas.
10. the pick-up unit for detecting gas concentration in water according to claim 9, it is characterized in that: described tested gas is carbon dioxide, the centre wavelength of the exciting light of the first LED light source (21) is 620nm, the centre wavelength of the exciting light of the second LED light source (22) is 430nm, and the reagent in reagent bag is BTB reagent.
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