CN105115921B - A kind of detection means for being used to detect gas concentration in water - Google Patents
A kind of detection means for being used to detect gas concentration in water Download PDFInfo
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- CN105115921B CN105115921B CN201510568145.6A CN201510568145A CN105115921B CN 105115921 B CN105115921 B CN 105115921B CN 201510568145 A CN201510568145 A CN 201510568145A CN 105115921 B CN105115921 B CN 105115921B
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- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention discloses a kind of detection means for being used to detect gas concentration in water.Its gas permeation tube and colorimetric pool are arranged at pump valve cabin and control out of my cabin；The inside and outside of pump valve cabin realizes pressure balance；Provided with bearing, microprocessor chip, opto-electronic conversion and I/V change-over circuits, A/D conversion chips, pump valve controlling switch circuit, the first and second LED/light sources, the first and second photodiodes and semi-transparent semi-reflecting lens in control cabinet, micro-flow pump, triple valve and two-way valve are provided with pump valve cabin；The inside intersection of " ten " the font passage of semi-transparent semi-reflecting lens on bearing.The exciting light of first, second LED/light source is divided into two-way through semi-transparent semi-reflecting lens, enter the first photodiode after wherein being partially absorbed all the way through the tested gas and the osmotic equilibrium liquid of reagent in colorimetric pool and form measurement signal, another road is directly entered the second photodiode and forms contrast signal, and the concentration of tested gas is obtained using measurement signal and contrast signal.
Description
Technical field
The present invention relates to a kind of detection means for being used to detect gas concentration in water.
Background technology
Detection for gases such as Oceanic Carbon Dioxide, methane, hydrogen sulfide is long-standing.Early in the 1950s, day
The scientist of the states such as sheet, the U.S., Britain begins to using gravimetric method and balances the nothing dissolved in the means such as pressure application measurement seawater
Machine carbon content.For example, traditional Oceanic Carbon Dioxide detection method mainly has Coulomb equation, gas chromatography and infrared spectroscopy
Photometry.
Coulomb equation is the detection method for being combined coulomb meter and patent electrolyte, and it is titrated molten using chemical reagent
Carbon dioxide quantity of the solution in coulomb pond.This method was proposed that its advantage is by Johnson K.M. et al. first in 1985
Using electricity as examination criteria, without primary standard substance, therefore higher sensitivity can be reached, but its pretreatment is complicated, and influence
Factor is more, up to tens kinds of its interfering ion, is difficult to control while titrating beginning and end, easily causes larger error；In addition, institute
The easily contaminated corrosion of electricity consumption, it is impossible to realize and measure for a long time.
Gas chromatography refers to the chromatography as order phase with gas, and it is for measuring the principle of seawater carbon dioxide such as
Under：Using air circulation pump, air on tested seawater sample and the sea level taken is set to reach pressure balance (in poised state
Under, it is believed that water sample is equal with air), the gas after balance is then passed through gas chromatographic analysis, chromatogram is obtained, finally
Calculated by a series of analyses, obtain the gas concentration lwevel of seawater.In recent years, with gas-chromatography isolation technics and related
The development of section, the detection performance of gas-chromatography has large increase, can reach higher precision, but it belongs to sampling analysis
Experimental determination is carried out after method, typically collecting sample, it is cumbersome, secondary pollution is easily brought, meanwhile, this method is to operation ring
Border requires harsh, and equipment is complicated, and required sample size is big, and time of measuring is long, it is impossible to meet the requirement of on-line monitoring.
The content of the invention
The purpose of the present invention is to overcome all or part of defect of prior art to be used to detect that gas is dense in water there is provided one kind
The detection means of degree.
To achieve the above object, the technical solution used in the present invention is：The present invention is used to detect gas concentration in water
Detection means includes the control cabinet of gas permeation tube, colorimetric pool, reagent bag, waste fluid bag, sealed pump valve cabin and resistance to hydrostatic pressure；Institute
State gas permeation tube and colorimetric pool is arranged at pump valve cabin and control out of my cabin；The pump valve cabin offers pump valve compartment, the pump valve cabin
Hole, which is sealed with balance film 57 in covering and pump valve cabin, to be full of silicone oil and makes to realize pressure balance inside and outside pump valve cabin；The control cabinet
It is interior to be provided with microprocessor chip, opto-electronic conversion and I/V change-over circuits, A/D conversion chips, pump valve controlling switch circuit, the first LED
Light source, the second LED/light source, the first photodiode, the second photodiode, bearing and semi-transparent semi-reflecting lens, the first LED/light source and
The centre wavelength of the exciting light of second LED/light source is different；Micro-flow pump, triple valve and two-way valve are provided with pump valve cabin；The light
Electricity conversion is electrically connected with first photodiode, the second photodiode respectively with the input of I/V change-over circuits, photoelectricity
Conversion is electrically connected with the output end of I/V change-over circuits with the input of A/D conversion chips, the output end of A/D conversion chips and institute
State the input electrical connection of microprocessor chip, input, the first LED/light source, the 2nd LED of the pump valve controlling switch circuit
Light source is electrically connected with the output end of microprocessor chip respectively；The triple valve, micro-flow pump, two-way valve respectively with pump valve control
The output end electrical connection of on-off circuit；The bearing is provided with " ten " font passage, and the semi-transparent semi-reflecting lens are placed in " ten "
The inside intersection of two sub-channels of font passage, the two ends port point of a wherein sub-channels for " ten " the font passage
She You not second LED/light source, second photodiode；It is somebody's turn to do one end of another sub-channels of " ten " font passage
Port is provided with first LED/light source, and the port of the other end of the subchannel and one end of incident optical are connected；The incident light
The fine other end is connected with the incident optical joint of the colorimetric pool, and the transmission fibre-optical splice of the colorimetric pool is by transmiting optical fiber
It is connected with first photodiode；The outlet of the entrance of the colorimetric pool and the gas permeation tube, the gas
The outlet of the entrance of osmos tube and the micro-flow pump, the import of the micro-flow pump and the public outlet of the triple valve
End connection a, entrance point of the triple valve is connected with reagent bag, the outlet and the import of the two-way valve of the colorimetric pool
End connection, the port of export of the two-way valve is connected with the waste fluid bag.
Further, present invention additionally comprises cleaning fluid bag, another entrance point of the cleaning fluid bag and the triple valve
Connection.
Further, present invention additionally comprises reagent cabin, the reagent bag and/or waste fluid bag are placed in the reagent cabin.
Further, present invention additionally comprises reagent cabin, in reagent bag, cleaning fluid bag, waste fluid bag any one or appoint
It is several to be placed in the reagent cabin.
Further, pin-saving chip, the input of the pin-saving chip are additionally provided with control cabinet of the present invention
End is electrically connected with the output end of the microprocessor chip.
Further, the output end 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 semi-transparent semi-reflecting lens of the present invention and two sub-channels of " ten " the font passage is
45°。
Further, the exciting light of the first LED/light source and the second LED/light source of the present invention enter colorimetric pool and by colorimetric
The osmotic equilibrium liquid of reagent and tested gas in pond absorption maximum effect can occur after absorbing.
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, the centre wavelength of the exciting light of the second LED/light source is that the reagent in 430nm, reagent bag is BTB reagents.
Compared with prior art, the beneficial effects of the invention are as follows：(1) present invention can by the carbon dioxide in water body,
The reagent of the tested gas sensitization such as methane, hydrogen sulfide is done with the osmotic equilibrium liquid of tested gas in the light absorption effect of certain wavelength
In-situ study, realizes and carries out in situ and on-line monitoring to the concentration of the gases such as the carbon dioxide in water body, methane, hydrogen sulfide, gram
The monitoring problem of gas concentration in water body can not be carried out under the conditions of the extreme pressures such as deep-sea by having taken prior art.(2) it is of the invention
Detection means realizes the osmotic equilibrium liquid of the different measurement periods phase before and after pipeline by the rational deployment of pump, valve and pipeline
The sequential flowing connect, so realize in water body be tested gas (such as carbon dioxide, methane) continuously monitor, with resistance to height
Pressure, broad quantum, sensitivity is high, simple to operate and the low advantage of testing cost, eliminate the secondary pollution of sample, sample frequency by
The shortcomings of limit, an effective approach is provided to solve the original position of tested gas and monitoring problem on-line.(3) present invention can disappear
Except the error brought surely due to flashing so that detection means of the present invention also has very high even if long-play under water
Measurement accuracy.
Brief description of the drawings
Fig. 1 is used for the structural representation for detecting the detection means of gas concentration in water for the present invention；
Fig. 2 is the structural representation of control module；
Fig. 3 is the connection diagram of detection means optical detecting module of the present invention and control module；
Fig. 4 is the schematic diagram of the gas collecting module of detection means of the present invention；
Fig. 5 gathers the schematic diagram of carbon dioxide in water body for the gas permeation tube of detection means of the present invention；
Fig. 6 is the structural representation of the lower cover in the pump valve cabin of detection means of the present invention；
Fig. 7 is the system response and standard two of the carbon dioxide obtained using detection means examination criteria water sample of the present invention
The corresponding relation curve of carbon oxide gas concentration.
In figure, 1. underwater electrical connectors, 2. control cabinets, the upper lid of 2a. control cabinets, the lower cover of 2b. control cabinets, 2c. control moulds
Block, 2d. bearings, 2e. batteries, 21. LED/light sources, 22. LED/light sources, 23. incident opticals, 23a. incident optical sealed pressing sleeves,
32. optical fiber is transmitted, 32a. transmission optical fiber sealed pressing sleeves, 24. first photodiodes, 25. second photodiodes, 26. is semi-transparent
Semi-reflective mirror, 3. colorimetric pools, 3a. incident optical joints, 3b. transmission fibre-optical splices, 3c. colorimetric pool entrances, the outlet of 3d. colorimetric pools,
3e.8 colorimetric pool fixed mounts, 3f. colorimetric pool fixed mounts, 35. discharge liquid pipes, 35a. discharge liquor seal of tube glands, the infiltration of 4. gases
Pipe, 4a. gas permeation tube entrances, the outlet of 4b. gas permeation tubes, 4c. copper mesh covers, 43. infiltration liquid pipes, 5. pump valve cabins, 5a. pump valves
The upper lid in cabin, the lower cover in 5b. pump valves cabin, 5c. fix bars, 5d. fix bars, 5e. watertight connecting lines, 51. triple valves, 52. miniflows
Measure pump, 53. two-way valves, 54. feed tubes, 54a. feed tube sealed pressing sleeves, 55. pump valve compartment, 56. balance film glands, 57. balances
Film, 6. reagent cabins, the lower cover in 6b. reagents cabin, 61. reagents bag, 61a. reagent connecting tubes, 61b. reagent connecting tube sealed pressing sleeves,
62. cleaning fluid bag, 62a. cleaning connecting tubes, 62b. cleaning connecting tube sealed pressing sleeves, 63. waste fluid bags, 63a. waste liquid connecting tubes,
63b. waste liquid connecting tube sealed pressing sleeves.
Embodiment
The present invention is further illustrated below in conjunction with the accompanying drawings.
As shown in figure 1, as one embodiment of the present invention, detection means of the present invention include 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 the upper lid 2a of control cabinet 2 center, the watertight for installing 6 cores in the through hole connects
Plug-in unit 1；It is fixedly connected between the lower cover 2b of control cabinet 2 and the upper lid 5a in pump valve cabin 5 by fix bar 5c with fix bar 5d；Reagent
The lower cover 5b in cabin 6 and pump valve cabin 5 is fixedly installed togather；Gas permeation tube 4 and colorimetric pool 3 are arranged at the outside of control cabinet 2.Its
In, the lower cover 2b of colorimetric pool 3 and control cabinet 2 is fixedly installed togather.Preferably, the present invention wraps gas using copper mesh cover 4c
Osmos tube 4, and also, it is fixedly connected by copper mesh cover 4c with the upper lid 5a in pump valve cabin 5 and consolidates gas permeation tube 4 with pump valve cabin 5
Dingan County is fitted together.During using detection means of the present invention, colorimetric pool 3 and gas permeation tube 4 are directly contacted with water body.Such as Fig. 5 institutes
Show that copper mesh cover 4c water-permeable and air permeables can avoid gas permeation tube 4 from being influenceed the osmotic efficiency of gas by biological attachment.Gas permeates
Pipe 4 only allows gas to penetrate through without allowing Liquid Penetrant to pass through tube wall.To utilize bromothymol blue reagent
Exemplified by the concentration of carbon dioxide in (Bromothymol Blue, abbreviation BTB reagent) detection water body, due to gas permeation tube 4
Gas is allowed to permeate without allowing Liquid Penetrant, therefore, during BTB reagents are stopped in gas permeation tube 4, in water body
Carbon dioxide gas, which is known from experience, to be penetrated into gas permeation tube 4 and occurs color change with BTB reagent reactings in gas permeation tube 4,
It is finally reached osmotic equilibrium；Then, osmotic equilibrium liquid enters in colorimetric pool 3 through permeating liquid pipe 43, and optics is completed in colorimetric pool 3
Detection, obtains corresponding metrical information.
In the embodiment shown in Fig. 1, detection means of the present invention is rendered as cylindrical shape in overall appearance, and structure is tight
Gather, and the weight of whole detection means can be reduced, it is 5kg or so to make its aerial weight, weight is 1kg or so under water.
The control cabinet 2 of the present invention, pump valve cabin 5, reagent cabin 6 can be processed into using pressure-resistant material (such as PEEK, POM).Control cabinet 2
Tubular shell, upper lid 2a, lower cover 2b thickness respectively may be about 10mm, and the internal diameter of tubular shell is aboutControl cabinet 2
Tubular shell two ends respectively with upper lid 2a, lower cover 2b by screw and O-ring seal sealing be fixedly installed togather.Control
The tolerable hydrostatic pressure for being not less than 3000m in cabin 2.To make detection means of the present invention reach the watertightness performance of 2000m under water, such as
Shown in Fig. 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 include bearing 2d, semi-transparent semi-reflecting lens 26, the first LED/light source 21,
Second LED/light source 22, the first photodiode 24, the 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, semi-transparent semi-reflecting lens 26, the first LED/light source 21, the second LED/light source 22,
One photodiode 24 and the second photodiode 25 are fixedly installed on bearing 2d.Bearing 2d is provided with " ten " font passage,
The port for 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 photoelectricity two respectively
Pole pipe 25, the port of one end of another sub-channels is installed with the first LED/light source 21, the other end port of the subchannel with
One end connection of incident optical 23；The other end of incident optical 23 is connected with the incident optical joint of colorimetric pool 3, colorimetric pool 3
Transmission fibre-optical splice is connected by transmiting optical fiber 32 with the first photodiode 24.To prevent outside body of water (such as seawater) from penetrating into control
In cabin 2 processed, as shown in figure 1, when incident optical 23 passes through the lower cover 2b of control cabinet, it is strict with incident optical sealed pressing sleeve 23a
Sealing；When transmission optical fiber 32 passes through the lower cover 2b of control cabinet, strictly sealed with transmission optical fiber sealed pressing sleeve 32a.In two strips
The inside intersection of passage is provided with semi-transparent semi-reflecting lens 26.The angle of the sub-channels of semi-transparent semi-reflecting lens 26 and two is respectively 45° angle,
So that the exciting light from the second LED/light source 22 is when by semi-transparent semi-reflecting lens 26, a semi-gloss is there are about through semi-transparent semi-reflecting lens 26
And received by the second photodiode 25 as contrast signal, second half light is reflected into incident optical by semi-transparent semi-reflecting lens 26
23 are used as optical signal transmissive；Similarly, the half that the exciting light from the first LED/light source 21 there are about reflected by semi-transparent semi-reflecting lens 26 and
Received by the second photodiode 25 as contrast signal, another semi-gloss is passed through to be made by semi-transparent semi-reflecting lens 26 into incident optical 23
For optical signal transmissive.Two-way optical signal transmissive is transmitted to colorimetric pool 3 through incident optical 23, during by colorimetric pool 3, by colorimetric pool 3
In the osmotic equilibrium liquid of reagent and tested gas absorb and be delivered to the pole of the first photoelectricity two via transmission optical fiber 32 again after a part
Pipe 24, is received by the first photodiode 24 and produces measurement signal.
As shown in Fig. 2 control module 2c may include microprocessor chip, opto-electronic conversion and I/V change-over circuits, A/D conversions
Chip, pump valve controlling switch circuit and pin-saving chip.Whole control module 2c can be integrated into one piece of pcb board and be fixedly mounted
On the upper lid 2a of control cabinet 2.Wherein, the input of opto-electronic conversion and I/V change-over circuits respectively with the first photodiode 24,
Second photodiode 25 is electrically connected, and opto-electronic conversion and the output end and the input of A/D conversion chips of I/V change-over circuits are electrically connected
Connect, the input of microprocessor chip is electrically connected with the output end of A/D conversion chips, the input of pump valve controlling switch circuit,
The output end electricity of the input of pin-saving chip, the first LED/light source 21, the second LED/light source 22 respectively with microprocessor chip
Connection；In addition, as shown in Figure 1, Figure 2 and Figure 4, triple valve 51, micro-flow pump 52, two-way valve 53 in pump valve cabin 5 pass through respectively
Watertight connecting line 5e is electrically connected with the output end of pump valve controlling switch circuit.
Battery 2e can be installed on control module 2c, so that detection means of the present invention is carried out independently by internal cell 2e
Power supply.Detection means of the present invention can be also connected by underwater electrical connector 1 and submerged cable with external powering device, so that by outside
It is powered.
As shown in figure 1, reagent bag 61, cleaning fluid bag 62 and waste fluid bag 63 are placed in reagent cabin 6, reagent bag 61, cleaning
Liquid bag 62 and waste fluid bag 63 can use the flexible package of Fresco Bag.Reagent cabin 6 is provided with opening, and outside water body can be entered by the opening
In reagent cabin 6, in addition, can also be easily to reagent bag 61, cleaning fluid bag 62 and waste fluid bag 63 and therein via the opening
Liquid is changed.As another embodiment of the invention, reagent cabin 6 can not be set, when measuring, by reagent bag
61st, cleaning fluid bag 62 and waste fluid bag 63 are placed directly within water body.
As shown in figure 1, pump valve cabin 5 is made up of the upper lid 5a in high voltage bearing housing and pump valve cabin and the lower cover 5b in pump valve cabin.
The upper lid 5a in pump valve cabin is fixedly connected with the lower cover 2b of control cabinet by fix bar 5c and fix bar 5d.As shown in fig. 6, in pump valve
There is pump valve compartment 55 on the lower cover 5b in cabin 5, the hole is diameterCircular hole, pump valve compartment 55 with balance film 57 it is (such as impermeable
The rubber or plastic sheeting of water) cover and with balance film gland 56 and CARBURIZING FURNACE FOR STAINLESS FASTENER fixing seal, thus make the interior of pump valve cabin 5
Portion is sealed environment, available for detecting gas concentration in 0-2000m water body.Due to being full of low viscosity silicon in pump valve cabin 5
Oil, and balance film 57 is flexible, when detection means of the present invention is placed in deep water, the hydrostatic pressure of outside body of water makes balance film
57 elasticity depression, make in the pump valve cabin 5 inside silicone oil generation identical hydrostatic pressure so that maintain the pump inside pump valve cabin 5, valve and
Pressure in its pipeline and the pressure complete one in gas permeation tube 4, colorimetric pool 3, reagent bag 61, cleaning fluid bag 62 and its pipeline
Cause and energy normal work.The internal and external pressure balance design of pressure-resistant design and pump valve cabin, reagent cabin due to control cabinet 2, sends out this
Bright whole detection means can be placed in the deep water within 2000m with cloth, it is ensured that pump, valve can be under different high hydrostatic pressures just
Often work.
Triple valve 51, micro-flow pump 52 and two-way valve 53 are placed in closed pump valve cabin 5.Wherein, triple valve 51, micrometeor
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 are respectively by through pump valve
The lower cover 5b in cabin 5 reagent connecting tube 61a, cleaning fluid bag connecting tube 62a is connected with two entrance points of triple valve 51, triple valve
The 51 public port of export and the inlet communication of micro-flow pump 52, the outlet of micro-flow pump 52 passes through feed tube 54 and gas permeation tube
4 gas permeation tube entrance 4a connections, the gas permeation tube outlet 4b of gas permeation tube 4 is entered by permeating liquid pipe 43 with colorimetric pool
Mouth 3c connections, colorimetric pool outlet 3d is connected by discharging liquid pipe 35 with the entrance point of two-way valve 53, and the port of export of two-way valve 53 leads to
Waste liquid connecting tube 63a is crossed to connect with waste fluid bag 63.Reagent connecting tube 61a, cleaning connecting tube 62a, waste liquid connecting tube 63a pass through pump
During the lower cover 5b in valve cabin, respectively with reagent connecting tube sealed pressing sleeve 61b, cleaning fluid connecting tube sealed pressing sleeve 62b, waste liquid connecting tube
Sealed pressing sleeve 63b is strictly sealed.Feed tube 54 and discharge liquid pipe 35 are close with feed tube respectively in the upper lid 5a through pump valve cabin
Envelope gland 54a and discharge liquor sealed pressing sleeve 35a is strictly sealed.In the present invention, triple valve 51 and micro-flow pump 52 can be selected respectively
With the three-way magnetic valve (LFRA2430110H) and micro-flow pump (LPLA1211050L) of LEE companies of the U.S..Micro-flow pump
(LPLA1211050L) it is 50 μ L often to act the liquid capacity once extracted.
When being measured using detection means of the present invention, the input of microprocessor chip and PC waterborne can be passed through water
Touch plug-in unit 1 and submerged cable electrical connection, so that control instruction is sent from PC waterborne to microprocessor chip, then by Wei Chu
Control instruction is transmitted to control pump valve controlling switch circuit, the first LED/light source 21 and the second LED/light source 22 by reason device chip, from
And microprocessor chip is controlled pump valve controlling switch circuit, the first LED/light source 21 and the second LED/light source according to the instruction of PC
22 are turned on and off.As another embodiment of the invention, also control can directly be sent by microprocessor chip itself
Instruction, control pump valve controlling switch circuit, the first LED/light source 21, the second LED/light source 22 are turned on and off.
Microprocessor chip controls micro-flow pump 52, triple valve 51, two-way valve by controlling pump valve controlling switch circuit
53 are turned on and off, so that select to open triple valve 51 and cleaning fluid bag 62 or the pipeline between reagent bag 61, and micro-
Cleaning fluid or reagent are extracted in the presence of flow pump 52.When selecting extraction reagent carries out gas concentration detection, triple valve 51
Cleaning fluid import is closed, and the reagent entry port of triple valve 51 is opened, and the reagent in reagent bag 61 is through reagent connecting tube 61a from triple valve
51 reagent entry port end enters triple valve 51, then enters micro-flow pump 52 from the public port of export of triple valve 51, then through feed liquor
Pipe 54 enters gas permeation tube 4, quilt of the reagent in gas permeation tube 4 with being penetrated by water body by gas permeation tube entrance 4a
Survey gas (such as carbon dioxide) mixing to reach after osmotic equilibrium, enter colorimetric pool through permeating liquid pipe 43 by gas permeation tube outlet 4b
3 carry out gas concentration detection, and the waste liquid after detection is finished exports 3d is transported to through discharge pipe 35 in pump valve cabin 5 two by colorimetric pool
Port valve 53, then by the outlet of two-way valve 53 through waste liquid connecting tube 63b enter reagent cabin in waste fluid bag 63 in.Thus, form
By reagent bag 61, the closing pipe line terminated to waste fluid bag 63.Because two-way valve 53 is located at the terminal of fluid path, when two-way valve 53
When being closed, it is ensured that avoid waste liquid from pouring in down a chimney and the pollution pipeline such as microorganism.
Microprocessor chip can select the MSP430F2XX series microprocessor chips of TI companies.Microprocessor chip is produced
The PWM ripples of certain frequency drive the first LED/light source 21 and the second LED/light source 22 to produce the exciting light with different wave length respectively.
For example, the first LED/light source 21 produces the exciting light that centre wavelength is 620nm, the second LED/light source 22 produces centre wavelength and is
430nm exciting light.Two beam exciting lights are divided into two-way after semi-transparent semi-reflecting lens 26, wherein being directly entered the pole of the second photoelectricity two all the way
Pipe 25 and obtain contrast signal；After another road absorbs via the osmotic equilibrium liquid of the reagent in colorimetric pool 3 and tested gas, finally
It is delivered to the first photodiode 24 and obtains measurement signal.First photodiode 24, the second photodiode 25 are received
To measurement signal and contrast signal by opto-electronic conversion and I/V change-over circuits be converted into direct current signal, then changed through 24 A/D
Chip is converted into data signal and sent to microprocessor chip, and digital signal information is transferred to data and deposited by microprocessor chip
Store up in chip (such as FLASH memory) and preserve.If the output end of pin-saving chip is passed through into underwater electrical connector 1 and submerged cable
It is connected with the PC of the water surface, the information that pin-saving chip is stored can be uploaded to PC when needed；Certainly, if necessary to right
Gas concentration in water body is monitored when putting into effect, and the PC of the water surface can also obtain the information stored in pin-saving chip in real time.
As another embodiment of the invention, the reality to the gas concentration in water body can also be realized without using pin-saving chip
When monitor on-line, i.e.,：, can be directly by underwater electrical connector 1 and electric under water by the output end of microprocessor chip when measuring
Cable is electrically connected with the PC of the water surface, so that the measurement data in microprocessor chip is directly uploaded into PC in real time.
It is left that the PWM ripples produced by microprocessor chip drive the first LED/light source 21 and the second LED/light source 22 to produce 2kHz
Right midband exchange light, realizes the detection of small-signal.The low power consumption characteristic of LED/light source, with luminosity stabilization, efficiency
High the advantages of.The ADS1246 chips of TI companies can be used in A/D conversion chips.ADS1246 chips are 24 high-precision A/D, highest
Output frequency reaches 2KSPS, and it is communicated by spi bus with microprocessor chip, and the output frequency for setting A/D is 5SPS, bipolar
Property sampling.FLASH memory AD45DB081B can be used in pin-saving chip.Microprocessor chip is by spi bus, by numeral
Signal is transferred in FLASH memory AD45DB081B and preserved.
As shown in figure 4, gas collecting module mainly includes：Microprocessor chip, pump valve controlling switch circuit, reagent bag
61st, cleaning fluid bag 62, triple 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.It is logical to complete the microprocessor chip in the in-situ acquisition of gas concentration lwevel information in water, control module 2c
Cross control pump valve controlling switch circuit to open triple valve 51 and micro-flow pump 52, so as to extract the BTB reagents in reagent bag 61.
BTB reagents are input in gas permeation tube 4 by micro-flow pump 52, BTB reagents stayed for some time in gas permeation tube 4 and with
The carbon dioxide penetrated from outside body of water combines and reaches osmotic equilibrium, then enters together in colorimetric pool 3.By enter than
Osmotic equilibrium liquid in optical signal transmissive from the first LED/light source 21 and the second LED/light source 22 collection colorimetric pool 3 in color pond 3
Light absorbs signal.When the tested gas in water be carbon dioxide, the exciting light of the first LED/light source 21 centre wavelength be
620nm, the centre wavelength of the exciting light of the second LED/light source 22 are reagent in 430nm, reagent bag when being BTB reagents, first
The exciting light of LED/light source and the second LED/light source enter colorimetric pool 3 and by the BTB reagents in colorimetric pool 3 and carbon dioxide
There is absorption maximum effect after absorbing in osmotic equilibrium liquid.
Illustrate the application method of detection means of the present invention with specific embodiment below：
(1) first, it can be cleaned before detection means of the present invention is put into water, preliminary examination.
The input of microprocessor chip is connected by underwater electrical connector and cable with outer PC, and by data storage
The output end of chip is connected by underwater electrical connector and cable with PC.It can be carried by underwater electrical connector by outside to detection means
For 12V power supplys or enable internal cell 2e.System initialization simultaneously reads systematic parameter, completes system boot.Microprocessor chip
The clear instruction of outer PC is received, micro-flow pump 52 and two-way valve 53 are opened by pump valve controlling switch circuit, and close three
The reagent entry port of port valve 51 and open its cleaning fluid import so that select by cleaning fluid bag 62 in cleaning fluid be pumped into triple valve
51, after successively via micro-flow pump 52, gas permeation tube 4, colorimetric pool, two-way valve 53, waste fluid bag 63, so as to clean whole pipe
Road.After the completion of cleaning, microprocessor chip receives the measurement instruction of outer PC, and miniflow is opened by pump valve controlling switch circuit
Pump 52 and two-way valve 53 are measured, and closes the cleaning fluid import of triple valve 51 and opens its reagent entry port, so that selecting extraction reagent
Into above-mentioned pipeline.Directly read the spectrophotometric value of the reagent in colorimetric pool 3.By taking BTB reagents as an example, in fluid path and colorimetric
In the case of bubble-free, free from admixture, light path are normal in pond, BTB reagents are in the first LED/light source 21 and the work of the second LED/light source 22
The ratio of spectrophotometric value under is less than 0.8, thus can substantially exclude and there is a situation where to cause measurement error (such as in pipeline
There are bubble, impurity etc. to influence the situation of accuracy of measurement).So far preliminary examination is completed.
(2) input of microprocessor chip is connected by cable in underwater electrical connector and water with water surface PC after,
And be connected the output end of pin-saving chip with water surface PC by cable in underwater electrical connector and water.Treat present invention detection dress
Put after the desired depth in water body, water surface PC sends measurement instruction to microcontroller chip, into the automatic measurement stage.
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
The μ L of osmotic equilibrium liquid about 100 stopped in 20cm, gas permeation tube 4, the length of infiltration liquid pipe 43 is about 15cm, permeates liquid pipe 43
The μ L of pipe inner capacities about 165.Microcontroller chip in control module 2c by pump valve controlling switch circuit control triple valve 51,
Micro-flow pump 52 and two-way valve 53 are turned on and off action, also, control the first LED/light source 21 and the by microprocessor chip
One LED/light source 22 carries out exciting action.
When a new measurement period starts, microcontroller chip opens micro- by controlling pump valve controlling switch circuit
The reagent entry port of flow pump 52, two-way valve 53 and triple valve 51.Micro-flow pump 52 is carried out continuously the action of 5 extraction novel agents,
Reagent 50 μ L are extracted every time, amount to 250 μ L 5 times.During the continuous drawing novel agent of micro-flow pump 52, novel agent also starts
Conveyed to gas permeation tube 4, meanwhile, the osmotic equilibrium to be detected for the upper measurement period formation retained in gas permeation tube 4
The liquid retained in liquid and infiltration liquid pipe 43 also begins to convey to colorimetric pool 3, retain in colorimetric pool 3 in upper one measurement
Cycle has detected that the osmotic equilibrium liquid (the osmotic equilibrium liquid of i.e. upper last measurement period formation) finished then starts to waste fluid bag 63
Direction is conveyed.
It should be noted that before the liquid retained in infiltration liquid pipe 43 starts to convey to colorimetric pool 3, permeating liquid pipe 43
Interior liquid is substantially the reagent without osmotic equilibrium that a upper measurement period is extracted, while allowing before infiltration liquid pipe 43
Section exist part not yet enter colorimetric pool 3 last measurement period extract reagent and gas osmotic equilibrium liquid and without
The reagent of osmotic equilibrium.Because infiltration liquid pipe 43 is located between colorimetric pool 3 and gas permeation tube 4, therefore, upper one measurement week
The osmotic equilibrium liquid to be detected of phase is reached before colorimetric pool 3, and the upper measurement period that original is resided in infiltration liquid pipe 43 is extracted
The reagent without osmotic equilibrium during flowing, in advance to the pipeline and colorimetric pool 3 that are passed through carried out rinse and
Purification, it is to avoid the Liquid Residue of the osmotic equilibrium liquid of upper last measurement period formation influences the to be detected of upper measurement period formation
The precision of the Concentration Testing of osmotic equilibrium liquid.
When extracting release 5 times of micro-flow pump 52, micro-flow pump 52, two-way valve 53 and triple valve 51 are closed.This
When, what is stopped in gas permeation tube 4 is entirely then full of upper in the novel agent (100 μ L) that this measurement period is extracted, colorimetric pool 3
The osmotic equilibrium liquid to be detected of one measurement period formation.Meanwhile, microprocessor chip instruction the light source of the first LED/light source 21 and
The exciting light of second LED/light source 22 generation exciting light, the light source of the first LED/light source 21 and the second LED/light source 22 is through semi-transparent semi-reflecting lens
The two-way optical signal transmissive obtained after 26 enters colorimetric pool 3 through incident optical 23, so that the upper measurement week in contrastive colours pond 3
The osmotic equilibrium liquid to be detected of phase carries out optical detection, while measurement data is stored to pin-saving chip or PC is sent to
Show and be further analysed processing.When the 100 μ L novel agents stopped in gas permeation tube 4 reach osmotic equilibrium, this is completed
Secondary measurement period.Then microcontroller chip opens micro-flow pump 52, two-way valve 53 and threeway by pump valve controlling switch circuit
The reagent entry port end of valve 51, into next measurement period.Thus, the present invention realize in water body gas concentration it is constant
Measurement.
It should be noted that when this measurement period is completed, what is stopped in gas permeation tube 4 is this survey to be detected
Reagent and the osmotic equilibrium liquid of gas that the amount cycle is extracted, what is stopped in colorimetric pool 3 is that this measurement period has been detected and finished
This survey is stopped in osmotic equilibrium liquid (reagent and the osmotic equilibrium liquid of gas that an i.e. upper measurement period is extracted), feed tube 54
The amount cycle extract reagent (without osmotic equilibrium), infiltration liquid pipe 43 in then stop have this measurement period extract without infiltration
The reagent of balance, and there may be the last measurement period extraction that part not yet enters colorimetric pool 3 in the leading portion of infiltration liquid pipe 43
Reagent and gas osmotic equilibrium liquid and reagent without osmotic equilibrium.
The osmotic equilibrium liquid to be detected of upper measurement period formation in each measurement period in contrastive colours pond 3 is carried out
The detailed process of optical detection is as follows：The PWM ripples produced by microprocessor chip drive the first LED/light source 21 and the second LED light
Source 22 produces the exciting light of different wave length respectively, for example, the first LED/light source 21 produces the excitaton source that centre wavelength is 620nm, the
Two LED/light sources 22 produce the exciting light that centre wavelength is 430nm.What the first LED/light source 21 and the second LED/light source 22 were produced excites
Light is each separated into through Beam and a branch of reflected light by semi-transparent semi-reflecting lens 26, wherein, the hair from the first LED/light source 21
Penetrate light and the transmitted light from the second LED/light source 22 is directly received by the second photodiode 25, thus correspond to and produce two ginsengs
According to signal (absorbance value) R21 and R22；Transmitted light from the first LED/light source 21 and the reflected light from the second LED/light source 22
Via incident optical 23 enter colorimetric pool 3, be saturated in colorimetric pool 3 after equilibrium liquid is partially absorbed pass through by transmission optical fiber 32 by
First photodiode 24 is received, and is thus corresponded to and is produced two measurement signal (absorbance value) M21 and M22.Measurement signal (M21,
M22) and contrast signal (R21, R22) is converted into direct current signal respectively through opto-electronic conversion and I/V change-over circuits, then through 24 AD
Conversion chip be converted into data signal, microprocessor chip is then transferred to again, by microprocessor chip by data signal M21,
M22, R21, R22 signal value and corresponding temporal information etc. are transferred to preservation in pin-saving chip (such as FLASH memory).
When calculating the gas concentration lwevel in tested water body, outer PC is from FLASH memory or directly from microprocessor
The measurement signal (M21, M22) at correspondence time point and the signal value of contrast signal (R21, R22) are read in device chip, with correspondence
The measurement signal value (absorbance value) of LED/light source subtracts contrast signal value (absorbance value) and obtains osmotic equilibrium liquid in two kinds of light
Light absorbs value difference A1 and A2 under source, i.e. A1=M21-R21, A2=M22-R22；By calculating A2 and A1 ratio A2/A1, just
The system response of tested gas concentration can be obtained.The table that the system response of foregoing tested gas concentration is pre-established for people
In the equation of bright system response and tested gas concentration corresponding relation, you can obtain the time of measuring point carbon dioxide it is dense
Angle value.Due to two kinds of respective measurement signal values of light source of calculating and the difference of contrast signal value can be passed through in measurement each time
Value is eliminated due to the error that flashing is brought surely so that detection means of the present invention also has even if long-play under water
Very high measurement accuracy.
It should be noted that before the concentration of tested gas is detected using detection means of the present invention, first with present invention dress
System response of the calibrating gas sample for measuring several concentration knowns in the range of 200-900ppm is put, so as to set up this
The normal equation of corresponding relation between system response and gas concentration obtained by invention detection means.Specifically, such as Fig. 7
It is shown, use apparatus of the present invention as Y-axis with the standard water sample concentration of known gas concentration lwevel in the range of 200-900ppm
Measure and standard water sample is carried out to detect that obtained system response A2/A1 is X-axis, drafting obtains apparatus of the present invention detection titanium dioxide
The standard curve of concentration of carbon.From the standard curve, direct proportionality between gas concentration and system response is tested.Profit
The linear fit coefficient correlation that calibration curve is set up with detection means of the present invention reaches 0.9915, illustrates detection means tool of the present invention
There is higher reliability.Can be further utilized according to the standard curve be tested gas obtained by detection means of the present invention be
The equation of corresponding relation between response of uniting and tested gas concentration.
As one embodiment of the present invention, the calculating process of the gas concentration lwevel in tested water body can also be direct
Completed in microprocessor chip.Then, the result of calculation of tested gas concentration is stored in data storage by microprocessor chip
In chip or directly by microprocessor chip be sent to the water surface PC carry out in real time show and read.It is stored in data storage core
The result of calculation of the tested gas concentration of piece can be then forwarded to PC when needed, also can be in real time sent to by pin-saving chip
PC is shown and read.
, can be with it should be noted that detection means of the present invention is except that can detect in water body in addition to the concentration of carbon dioxide
Concentration for detecting the gas of other in water body (such as methane, hydrogen sulfide).Those skilled in the art can utilize prior art
Knowledge, reagent and the first LED/light source and the 2nd LED that match according to used in being determined the specific gas to be detected
The centre wavelength of light source, its criterion is with the first LED/light source and the exciting light of the second LED/light source in entrance colorimetric pool 3
Absorption maximum effect can occur after being absorbed by the osmotic equilibrium liquid of the tested gas in colorimetric pool and reagent to be advisable.
Claims (17)
1. a kind of detection means for being used to detect gas concentration in water, it is characterised in that：Including gas permeation tube（4）, colorimetric pool
（3）, reagent bag（61）, waste fluid bag（63）, sealed pump valve cabin（5）With the control cabinet of resistance to hydrostatic pressure（2）；The gas permeation tube
（4）And colorimetric pool（3）It is arranged at pump valve cabin（5）And control cabinet（2）Outside；The pump valve cabin（5）Offer pump valve compartment（55）, should
Pump valve compartment（55）Use balance film（57）Sealing covering and pump valve cabin（5）It is interior to make pump valve cabin full of silicone oil（5）Inside and outside realization
Pressure balance；The control cabinet（2）It is interior provided with microprocessor chip, opto-electronic conversion and I/V change-over circuits, A/D conversion chips,
Pump valve controlling switch circuit, the first LED/light source（21）, the second LED/light source（22）, the first photodiode（24）, the second photoelectricity
Diode（25）, bearing（2d）And semi-transparent semi-reflecting lens（26）, the first LED/light source（21）With the second LED/light source（22）Exciting light
Centre wavelength it is different；Pump valve cabin（5）It is interior to be provided with micro-flow pump（52）, triple valve（51）And two-way valve（53）；The photoelectricity turns
Change with the inputs of I/V change-over circuits respectively with first photodiode（24）, the second photodiode（25）It is electrically connected
Connect, opto-electronic conversion is electrically connected with the output end of I/V change-over circuits with the input of A/D conversion chips, A/D conversion chips it is defeated
Go out end to electrically connect with the input of the microprocessor chip, input, the first LED/light source of the pump valve controlling switch circuit
（21）, the second LED/light source（22）Electrically connected respectively with the output end of microprocessor chip；The triple valve（51）, micro-flow pump
（52）, two-way valve（53）The output end with pump valve controlling switch circuit is electrically connected respectively；The bearing（2d）It is provided with " ten " word
Type passage, the semi-transparent semi-reflecting lens（26）The inside intersection of two sub-channels of described " ten " font passage is placed in, it is described
The two ends port of a wherein sub-channels of " ten " font passage is respectively equipped with second LED/light source（22）, second light
Electric diode（25）；The port for being somebody's turn to do one end of another sub-channels of " ten " font passage is provided with first LED/light source（21）,
The port of the other end of the subchannel and incident optical（23）One end connection；The incident optical（23）The other end with it is described
Colorimetric pool（3）Incident optical joint connection, the colorimetric pool（3）Transmission fibre-optical splice by transmiting optical fiber（32）With it is described
First photodiode（24）Connection；The colorimetric pool（3）Entrance and the gas permeation tube（4）Outlet, it is described
Gas permeation tube（4）Entrance and the micro-flow pump（52）Outlet, the micro-flow pump（52）Import with it is described
Triple valve（51）The public port of export connection, the triple valve（51）An entrance point and reagent bag connect, the colorimetric pool
（3）Outlet and the two-way valve（53）Entrance point connection, the two-way valve（53）The port of export connected with the waste fluid bag.
2. the detection means according to claim 1 for being used to detect gas concentration in water, it is characterised in that：Also include cleaning
Liquid bag（62）, cleaning fluid bag and the triple valve（51）Another entrance point connection.
3. the detection means according to claim 1 for being used to detect gas concentration in water, it is characterised in that：Also include reagent
Cabin（6）, the reagent bag（61）And/or waste fluid bag（63）It is placed in the reagent cabin.
4. the detection means according to claim 2 for being used to detect gas concentration in water, it is characterised in that：Also include reagent
Cabin（6）, the reagent bag（61）, cleaning fluid bag（62）, waste fluid bag（63）In any one or appoint and several be placed in the reagent cabin
It is interior.
5. the detection means according to any one of claim 1 to 4 for being used to detect gas concentration in water, its feature exists
In：The control cabinet（2）Inside it is additionally provided with pin-saving chip, the input of the pin-saving chip and the microprocessor core
The output end electrical connection of piece.
6. the detection means according to claim 5 for being used to detect gas concentration in water, it is characterised in that：The data are deposited
The output end for storing up chip is connected with outside PC.
7. being used for according to claim 1,2,3,4 or 6 detects the detection means of gas concentration in water, it is characterised in that：
The microprocessor chip is connected with outside PC.
8. the detection means according to claim 5 for being used to detect gas concentration in water, it is characterised in that：The microprocessor
Device chip is connected with outside PC.
9. being used for according to claim 1,2,3,4,6 or 8 detects the detection means of gas concentration in water, its feature exists
In：The semi-transparent semi-reflecting lens（26）Angle with two sub-channels of " ten " the font passage is 45 °.
10. the detection means according to claim 5 for being used to detect gas concentration in water, it is characterised in that：It is described semi-transparent
Semi-reflective mirror（26）Angle with two sub-channels of " ten " the font passage is 45 °.
11. the detection means according to claim 7 for being used to detect gas concentration in water, it is characterised in that：It is described semi-transparent
Semi-reflective mirror（26）Angle with two sub-channels of " ten " the font passage is 45 °.
12. being used for according to claim 1,2,3,4,6,8,10 or 11 detects the detection means of gas concentration in water, its
It is characterised by：The exciting light of first LED/light source and the second LED/light source enters colorimetric pool（3）And by colorimetric pool（3）In examination
The osmotic equilibrium liquid of agent and tested gas absorption maximum effect can occur after absorbing.
13. the detection means according to claim 5 for being used to detect gas concentration in water, it is characterised in that：Described first
The exciting light of LED/light source and the second LED/light source enters colorimetric pool（3）And by colorimetric pool（3）In reagent and tested gas ooze
Saturating equilibrium liquid absorption maximum effect can occur after absorbing.
14. the detection means according to claim 7 for being used to detect gas concentration in water, it is characterised in that：Described first
The exciting light of LED/light source and the second LED/light source enters colorimetric pool（3）And by colorimetric pool（3）In reagent and tested gas ooze
Saturating equilibrium liquid absorption maximum effect can occur after absorbing.
15. the detection means according to claim 9 for being used to detect gas concentration in water, it is characterised in that：Described first
The exciting light of LED/light source and the second LED/light source enters colorimetric pool（3）And by colorimetric pool（3）In reagent and tested gas ooze
Saturating equilibrium liquid absorption maximum effect can occur after absorbing.
16. the detection means according to claim 12 for being used to detect gas concentration in water, it is characterised in that:The quilt
Survey gas is carbon dioxide, the first LED/light source（21）Exciting light centre wavelength be 620nm, the second LED/light source（22）Swash
Luminous centre wavelength is that the reagent in 430nm, reagent bag is BTB reagents.
17. being used for according to claim 13,14 or 15 detects the detection means of gas concentration in water, it is characterised in that:
The tested gas is carbon dioxide, the first LED/light source（21）Exciting light centre wavelength be 620nm, the second LED/light source
（22）Exciting light centre wavelength be 430nm, reagent bag in reagent be BTB reagents.
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| US9192707B2 (en) | 2011-04-29 | 2015-11-24 | Medtronic, Inc. | Electrolyte and pH monitoring for fluid removal processes |
| US11313804B2 (en) | 2016-09-09 | 2022-04-26 | Medtronic, Inc | Fluid sensor apparatus |
| US11255831B2 (en) | 2016-09-09 | 2022-02-22 | Medtronic, Inc. | Colorimetric gas detection |
| US11013843B2 (en) | 2016-09-09 | 2021-05-25 | Medtronic, Inc. | Peritoneal dialysis fluid testing system |
| DE102018122216A1 (en) * | 2018-09-12 | 2020-03-12 | SIKA Dr. Siebert & Kühn GmbH & Co. KG | Flow-through tube insert for optical flow measurement |
| CN111489627B (en) * | 2020-03-26 | 2021-09-24 | 南方海洋科学与工程广东省实验室(广州) | System for simulating ocean cold spring development and implementation method thereof |
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