CN103091262B - Miniaturized optical device for detecting ammonia nitrogen in water and detecting method - Google Patents
Miniaturized optical device for detecting ammonia nitrogen in water and detecting method Download PDFInfo
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- CN103091262B CN103091262B CN201110345310.3A CN201110345310A CN103091262B CN 103091262 B CN103091262 B CN 103091262B CN 201110345310 A CN201110345310 A CN 201110345310A CN 103091262 B CN103091262 B CN 103091262B
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Abstract
The invention discloses a miniaturized optical device for detecting ammonia nitrogen in water and a detecting method, and relates to water quality detection technology. A gas-liquid separation unit comprises a bowl-shaped water tank, a tank cover, a peristaltic pump, a four-way valve and connecting pipes, wherein one end of the peristaltic pump is connected with the water tank through a first connecting pipe, the other end of the peristaltic pump is connected with one end of the four-way valve through a second connecting pipe. An optical detection unit comprises an air chamber, at least one light source, at least one photo-detector, and at least one ammonia gas sensing element, wherein the light source is located at one inner side wall of the air chamber, the photo-detector is located the other inner side wall of the air chamber and is opposite the light source, the ammonia gas sensing element is located between the light source and the photo-detector, and an upper end of the ammonia gas sensing element is fixedly connected with a top wall of the air chamber. The light from the light source vertically passes through the ammonia gas sensing element on an optical path of the light source and then is received by the photo-detector. An output end of a signal processing chip is electrically connected with subsequent devices. The device is simple in structure, small in size and wide in detection range, and the ammonia gas sensing element can be repeatedly used, and thus the device is suitable for on-site quick detection.
Description
Technical field
The present invention relates to water quality inspection technique field, be a kind of miniaturized optical formula Water quality ammonia nitrogen pick-up unit, on-the-spot rapid and accurate determination can be carried out to the ammonia-nitrogen content in water sample to be measured.
Background technology
In water, ammonia nitrogen mainly exists with free ammonia and ammonium salt two kinds of forms, its main source is decomposition product, some industrial waste water that in sanitary sewage, itrogenous organic substance is subject to microbial action, as superfluous feed in curriery waste water, coking chemical waste water and synthetic ammonia chemical fertilizer factory waste water, agricultural drain, aquaculture water and fish, a large amount of excremental accumulation of shrimp and excessive fertilising etc.In addition, in oxygen-free environment, the nitrite existed in water also can be subject to microbial action, is reduced to ammonia.
In water, the harmfulness of ammonia nitrogen is large.Free ammonia is the principal element causing hydrobiont to poison, large tens times of its toxicity ratio ammonium salt, and increases with the enhancing of water body alkalescence.Ammonia nitrogen toxicity and water pH value and water temperature have substantial connection, generalized case, and temperature and pH value are higher, and toxicity is stronger.Toxic action about free ammonia it is generally acknowledged that non-free ammonia infiltrates in biosome, and reduce the oxygen carrying capability of blood, biological breathing function is declined, and secondly its primary attack body mucous membrane is nervous system.In addition, ammonia nitrogen as water nutrition pollutant, in water body content comparatively Gao Shihui cause water quality deterioration, the ecosystem is unbalance, cause eutrophication harm.Cause the amount reproduction of algae and microorganism, the dissolved oxygen DO in water consumes excessively, and reoxygenation speed is significantly less than oxygen, consumption efficiency, finally causes the death that fish are a large amount of, even occurs the dry destruction in lake.
Due to the above-mentioned harm of ammonia nitrogen, quick and precisely detect very important to the scene of carrying out ammonia-nitrogen content in the water bodys such as industrial waste water, sanitary sewage, underground water, reservoir water factory rivers and lakes.According to the instant data of ammonia-nitrogen content in water to take appropriate measures, guarantee that the ammonia-nitrogen content of rivers and lakes and enterprise wastewater discharge is within safety index.At present, Water quality ammonia nitrogen method for measuring mainly contains reagent colorimetric method, salicylic acid-hypochlorite colourimetry, Ammonia Gas Sensor Electrode Method, neutralization titration, gas-phase molecular absorption spectrometry method, Ammonia recovery determination method.Wherein first two method becomes the standard method of ammonia nitrogen determination in " state environment protecting standard " water quality., these existing ammonia nitrogen detection method still existing defects.Such as, reagent colorimetric method, salicylic acid-hypochlorite colorimetric and neutralization titration use reagent more, complex operation, water sample needs pre-service, test duration is long, is not suitable for the weak points such as field quick detection, and first two colourimetry also needs to use large-scale spectrophotometer; Although the quick electrode method of ammonia does not need water sample pre-service, electrode structure is complicated, and poor stability, is easily disturbed, and needs frequent calibration; Gas-phase molecular absorption spectrometry method needs to use expensive spectrometer, and needs longer light path to ensure higher sensitivity, is therefore not easy to the miniaturization of detecting instrument and portable, thus makes this side's kind method be not suitable for Site Detection; Ammonia recovery determination method utilizes the ammonia of absorbing pure water water sample alkalization release, then adds the absorbance after acid base indicator mensuration absorbing pure water ammonia, the shortcomings such as this method also exists complex operation, and equipment is complicated.Except the detection method of above-mentioned routine, have also appeared the reagent strip and kit that detect for Water quality ammonia nitrogen in recent years, although these simple and easy method detection speeds are fast, poor accuracy, is not suitable for quantitative measurement.
Summary of the invention
The object of the present invention is to provide a kind of miniaturized optical formula Water quality ammonia nitrogen pick-up unit, structure is simple, easy and simple to handle, volume is little, lightweight, be easy to carry, sensitive height, broad quantum, existing similar main equipment can be replaced, realize the on-the-spot rapid and accurate determination of the ammonia-nitrogen content to different water environment.
For achieving the above object, technical solution of the present invention is:
A kind of miniaturized optical formula Water quality ammonia nitrogen pick-up unit, it comprises a gas-liquid separation unit, an optical detection unit, a signal processing chip; Wherein:
Gas-liquid separation unit comprises a bowl-shape tank, a groove lid, a peristaltic pump, a four-way valve and connecting duct; The Single port of peristaltic pump is through the first connecting duct connection water channel, and another port second connecting duct connects four-way valve Single port;
Optical detection unit comprises a bowl-shape air chamber, at least one light source, at least one photo-detector, at least one ammonia sensitive element; Light source is positioned at air chamber madial wall, and photo-detector is positioned at another madial wall of air chamber, just right with light source; Ammonia sensitive element is positioned in the middle of light source and photo-detector, and upper end is fixed in air chamber inner roof wall, in the light path of light source, light source light is vertically received by photo-detector through after ammonia sensitive element;
Tank under, air chamber upper, tank opening seals with air chamber opening and docks, and by-level sets firmly groove lid, and groove covers and is provided with multiple micro-through-hole, makes the gas of the gentle indoor of tank can phase counterdiffusion;
Another three ports connection air chamber of four-way valve, one connects catheter, and one is unsettled for subsequent use; The catheter other end and water sample to be measured or annex solution container interlink, for water sample to be measured or annex solution are injected, discharge tank;
Photo-detector exports and is electrically connected with outside signal processing chip input end, and signal processing chip output terminal is electrically connected on follow-up equipment.
Described miniaturized optical formula Water quality ammonia nitrogen pick-up unit, air chamber described in it is made up of the light-proof material of metal, black plastic; Tank, groove lid and four-way valve are made up of organic glass, teflon alkali resistant materials, and wherein, groove lid uses light-proof material.
Described miniaturized optical formula Water quality ammonia nitrogen pick-up unit, ammonia sensitive element described in it, comprise light tight fixture, printing opacity and meet the sensitive diaphragm of ammonia generation color change, two jig arm centers of light tight fixture respectively have a through hole, two through hole is relative, ammonia sensitive diaphragm is entirely placed in two jig arm intermediate groove, and covers the through hole in two jig arm completely;
The through hole that light tight fixture two jig arm is opened, respectively just to light source, photo-detector, makes light source light pass after ammonia sensitive diaphragm through relative through hole, is radiated at photo-detector receiving end.
Described miniaturized optical formula Water quality ammonia nitrogen pick-up unit, ammonia sensitive diaphragm described in it, for porous structure, with fritted glass, porous filter paper or porous polymer, one of them makes, and has and can react the chemical substance of variable color at normal temperatures and pressures with ammonia in hole: polyaniline, thymol blue, bromthymol blue one of them.
Described miniaturized optical formula Water quality ammonia nitrogen pick-up unit, annex solution described in it, for concentration is not less than NaOH or the KOH aqueous solution of 1 mol/L.
Described miniaturized optical formula Water quality ammonia nitrogen pick-up unit, tank diapire described in it has a through hole, one end of through hole and the first connecting duct is tightly connected, the other end and the peristaltic pump Single port of the first connecting duct are tightly connected, and peristaltic pump another port second connecting duct and four-way valve Single port are tightly connected.
Described miniaturized optical formula Water quality ammonia nitrogen pick-up unit, air chamber inner roof wall described in it has a through hole, through hole is tightly connected through the 3rd connecting duct and four-way valve Single port, makes the air in air chamber back and forth be pumped in tank or air chamber by four-way valve and peristaltic pump; Air chamber madial wall is provided with groove, and with fixed light source, photo-detector, electrical connection place that light source and photo-detector pass air chamber wall seals with glue; Air chamber inner roof wall is provided with holder, and it is affixed that the light tight fixture upper end of ammonia sensitive element is arranged in holder, and ammonia sensitive element vertically downward, is positioned in the light path of light source.
Described miniaturized optical formula Water quality ammonia nitrogen pick-up unit, peristaltic pump described in it is two-way peristaltic pump.
Described miniaturized optical formula Water quality ammonia nitrogen pick-up unit, catheter described in it, for silicon rubber or polytetrafluoroethylmaterial material make, for injecting and discharging water sample to be measured or annex solution; Regulate four-way valve after opening peristaltic pump, when rotating forward, water sample to be measured or annex solution can be injected into tank, during reversion, peristaltic pump makes water sample to be measured or annex solution discharge tank.
Described miniaturized optical formula Water quality ammonia nitrogen pick-up unit, light source described in it, the absorption spectrum ranges that its emission wavelength produces after being positioned at the variable color of ammonia sensitive element; Photo-detector, be the light activated photodiode that sends light source or photoelectric cell, the output electric signal of this detector is linear with the light intensity be radiated on photo-detector.
Described miniaturized optical formula Water quality ammonia nitrogen pick-up unit, it is in same air chamber, one optical detecting channel and an optics reference channel are set, optical detecting channel is by a light source, one photo-detector and ammonia sensitive element composition, optics reference channel is by a light source, one photo-detector, with a reference elements composition, reference elements is identical with ammonia sensitive element structure, do not add in the perforated membrane film perforation that difference is only reference elements fill can with the perforated membrane film perforation of the chemical substance of ammonia gas react variable color and sensitive element in add be filled with can with the chemical substance of ammonia gas react variable color.Difference measurement is carried out to the photodetector output signal of optics reference channel and the photodetector output signal of optical detecting channel.
Described miniaturized optical formula Water quality ammonia nitrogen pick-up unit, it is in same air chamber, multiple light source, multiple photo-detector, multiple ammonia sensitive element are set, each light source, a photo-detector, an ammonia sensitive element form an optical detecting channel, form multiple optical detecting channel thus, sensitive diaphragm thickness in the ammonia sensitive element of each sense channel is different, expands pick-up unit thus to the measurement range of Water quality ammonia nitrogen, realizes many precision, multirange detects.
Described miniaturized optical formula Water quality ammonia nitrogen pick-up unit, peristaltic pump belonging to it and four-way valve are manually got liquid in employing and are replaced to be replaced by a micro air pump when automatically getting liquid.Micro air pump air intake opening is tightly connected through the first connecting duct and air chamber inner roof wall through hole, micro air pump gas outlet be tightly connected through the 3rd connecting duct and tank diapire through hole.Air in air chamber is back and forth pumped in tank by micro air pump.Manually getting liquid uses syringe to complete.During fluid injection, first connecting duct is separated with air chamber inner roof wall through hole, then water sample to be measured or annex solution are injected in tank through air chamber inner roof wall through hole and groove lid micropore by syringe needle, remove needle and syringe head fast afterwards and the first connecting duct and air chamber inner roof wall through hole are tightly connected.
The detection method of described miniaturized optical formula Water quality ammonia nitrogen pick-up unit, its flow process is:
Steps A) make the standard database of ammonia nitrogen concentration;
Step B) regulate four-way valve, open peristaltic pump and rotate forward, in tank, pump into the water sample to be measured that a volume is 1 to 8 milliliter, then switch four-way valve and make gas in air chamber pump into tank;
Step C) power to photo-detector, signal processing chip and follow-up equipment, the background signal of harvester before opening light source;
Step D) open light source, and monitor light source light through the light intensity change after ammonia sensitive element until photodetector output signal changes no longer in time;
Step e) switch four-way valve and volume is 1 to 5 milliliter and the annex solution that concentration is not less than the NaOH aqueous solution of 1 mol/L pumps into tank, the pH value of liquid in tank is made to be greater than 11, and then switching four-way valve makes gas in air chamber pump into tank, continuous acquisition photodetector output signal simultaneously;
Step F) stop test when observing after photodetector signal changes no longer in time, then switch four-way valve and make peristaltic pump reverse rotation to discharge the liquid in tank;
Step G) after the liquid in tank is thoroughly discharged, switch four-way valve and under peristaltic pump drives, enter air chamber from the pore of air chamber by outside air, ammonia sensitive element is replied, or separated gas chamber and tank, allow ammonia sensitive element be exposed in air automatically reply, to use next time;
Step H) result recorded is carried out processing after and steps A) the normal data database data that makes compares, to obtain the ammonia nitrogen concentration in water sample to be measured.
The invention has the advantages that: affiliated miniaturized optical formula Water quality ammonia nitrogen structure of the detecting device is simple, make easily, easy and simple to handle, volume is little, lightweight, be easy to carry, highly sensitive, broad quantum, detection limit is low, and antijamming capability is strong, and water sample does not need pre-service, ammonia sensitive element is reusable, is suitable for carrying out field quick detection to the ammonia-nitrogen content of the water environments such as river, lake, reservoir, plant chimney stalk, sanitary sewage, water station, water treatment plant.
Accompanying drawing explanation
Fig. 1 is the structural representation of a kind of miniaturized optical formula Water quality ammonia nitrogen pick-up unit of the present invention;
Fig. 2 be miniaturized optical formula Water quality ammonia nitrogen pick-up unit of the present invention use ammonia sensitive element before combining with combination after schematic diagram;
Fig. 3 is the absorbance curve over time under variable concentrations aqueous ammonium chloride solution sample utilizing miniaturized optical formula Water quality ammonia nitrogen pick-up unit of the present invention to record;
Fig. 4 is the relation of the ammonium chloride concentration (or nitrogen content) of absorbance and the detected water sample utilizing miniaturized optical formula Water quality ammonia nitrogen pick-up unit of the present invention to record;
Fig. 5 is the absorbance curve over time under variable concentrations aqueous ammonium chloride solution sample recorded after utilizing miniaturized optical formula Water quality ammonia nitrogen pick-up unit of the present invention to replace peristaltic pump and four-way valve assembly by micro air pump under the mode of manual fluid injection.
Embodiment
A kind of miniaturized optical formula Water quality ammonia nitrogen pick-up unit of the present invention is the ammonia-nitrogen content obtained by utilize optical means to detect in confined space ammonia concentration that water sample to be measured discharges under highly basic condition in water sample.This device mainly comprises a gas-liquid separation unit, an optical detection unit and a signal processing chip.
Fig. 1 is the structural representation of miniaturized optical formula Water quality ammonia nitrogen pick-up unit of the present invention, Fig. 2 be miniaturized optical formula Water quality ammonia nitrogen pick-up unit of the present invention use ammonia sensitive element before combining with combination after schematic diagram.In figure, 1 is air chamber, and 11 is air chamber through hole, and 2 is tank, 21 is tank through hole, and 3 is groove lid, and 31 is groove lid through hole, 4 is ammonia sensitive element, and 41 is sensitive diaphragm, and 42 is light tight fixture, 43 is Folder through-holes, and 5 is light source, and 6 is photo-detector, 7 is signal processing chip, and 8 is peristaltic pump, and 9 is four-way valve, 91 to 94 four ports being respectively four-way valve, 10 is connecting duct, and 11 is solution bottle.
The gas-liquid separation unit of pick-up unit of the present invention is made up of tank 2, groove lid 3, two-way peristaltic pump 8, four-way valve 9 and connecting duct 10, and optical detection unit is made up of air chamber 1 and the single or multiple optical profile type ammonia detection channels be arranged in air chamber 1.Each detection channels comprises light source 5, photo-detector 6 and ammonia sensitive element 4, and the light that light source 5 sends vertically is received by photo-detector 6 through after ammonia sensitive element 4.Photo-detector 6 output terminal of each detection channels is electrically connected with signal processing chip 7.Tank 2 is placed in below air chamber 1 and both seal docking, and centre is provided with groove lid 3.Gas in tank 2 and air chamber 1 can by the micro-through-hole 31 phase counterdiffusion that groove lid 3 is offered; The through hole 21 that the inner bottom surface of tank 2 is offered is tightly connected with the Single port of peristaltic pump 8, for injection and the discharge of liquid or gas; Another port and the four-way valve port 92 of peristaltic pump 8 are tightly connected; Four-way valve port 91 and air chamber through hole 11 are tightly connected, and port 93 connects woven hose, for the water sample to be measured in solution bottle 11 or NaOH annex solution are injected tank 2, also the waste liquid in tank 2 can be discharged in solution bottle 11; Four-way valve port 94 is unsettled for subsequent use.
The ammonia sensitive element 4 that pick-up unit of the present invention uses is made up of the ammonia sensitive diaphragm 41 of light tight fixture 42 and printing opacity, through hole 43 is offered at light tight fixture 42 center, ammonia sensitive diaphragm 41 is entirely placed in the middle of light tight fixture 42, and covers through hole 43 completely.Ammonia sensitive diaphragm 41 is porous structure, as fritted glass, porous filter paper and porous polymer etc., is provided with and can reacts the chemical substance of variable color at normal temperatures and pressures, as polyaniline, thymol blue, bromthymol blue etc. with ammonia in hole.
Following examples set forth a kind of typical apply mode and the running program of miniaturized optical formula Water quality ammonia nitrogen pick-up unit of the present invention:
1, the preparation of ammonia sensitive element 4:
Ammonia sensitive diaphragm 41 prepared is in this example made by fritted glass fiber disk, and selected fritted glass fiber disk diameter is 10mm, and thickness is 1mm.With bromthymol blue (BTB) solution of anhydrous alcohol preparation 4g/L, use pipettor to get 150 microlitre BTB solution to drip on fritted glass fiber disk, it is made all to soak, after being placed on shading place natural drying, be placed in the middle of fixture 42 by method shown in Fig. 2 and form ammonia sensitive element 4, for subsequent use in the detection thorough fare that this element is arranged on air chamber 1.
2, water sample ammonia nitrogen detects:
The present embodiment uses the miniaturized optical formula Water quality ammonia nitrogen pick-up unit shown in Fig. 1, wherein light source 5 adopts wavelength to be the light emitting diode of 625 ± 5nm, photo-detector 6 adopts the silicon photoelectric diode chip with pre-amplification circuit, and signal processing chip 7 is commercially available high-accuracy data collection card.
With the NH of deionized water preparation 100mg/L
4c1 solution, and then the solution being diluted to variable concentrations (0.01mg/L-10mg/L) with deionized water, as water sample to be measured.The NaOH solution of 1mol/L is prepared as annex solution with deionized water.
During test, regulate four-way valve 9, and open peristaltic pump 8,8 milliliters of water samples to be measured are pumped in tank 2, switching four-way valve 9 makes the gas circulator in air chamber 1 enter tank 2, power then to photo-detector 6, signal processing chip 7 and follow-up equipment, before unlatching light source 5, gather 5-minute data, obtain bias light intensity (I
d); Open light source 5, observe that photodetector output signal gathers a minute data after stable, obtain initial light intensity degree (I
0); Switch four-way valve 9 and 2 milliliters of NaOH annex solutions are pumped into tank 2, again switch four-way valve 9 and make the gas circulator in air chamber 1 enter tank 2, and the output signal (I of continuous acquisition photo-detector 6
s), length of testing speech is 1 hour.According to the transmitted intensity (I recorded
s) calculate not absorbance in the same time over time.Absorbance (A) is defined as:
After test terminates, switch four-way valve 9 and make peristaltic pump 8 reverse rotation to discharge the liquid in tank 2.After the liquid in tank 2 is thoroughly discharged, pump into 10ml pure water cleaning sink 2, then by water pump water outlet groove 2, switch four-way valve 9 afterwards to allow outside air enter air chamber 1 from air chamber pore 11 under the driving of peristaltic pump 8 ammonia sensitive element 4 is replied, or separated gas chamber 1 and tank 2, allow ammonia sensitive element 4 be exposed in air automatically reply, to use next time.
The absorbance curve over time that Fig. 3 records respectively for utilizing the pick-up unit shown in Fig. 1 under eight kinds of ammonium chloride concentrations.Before adding NaOH, ammonia sensitive diaphragm 41 pairs of wavelength are that the absorption of the light of 625nm is almost nil, and therefore absorbance is close to zero; After adding NaOH, in the ammonia of water sample release and sensitive diaphragm 41, the quick reagent reacting of ammonia that arranges generates blue material, make sensitive diaphragm 41 pairs of wavelength be 625nm light produce strong absorption, therefore absorbance start raise until in air chamber 1 ammonia concentration no longer change.Fig. 4 is the relation of the ammonium chloride concentration (or nitrogen content) of absorbance and the detected water sample utilizing miniaturized optical formula Water quality ammonia nitrogen pick-up unit of the present invention to record, as can be seen from the figure when ammonium chloride concentration is greater than 1 mg/litre, the absorbance recorded at given time becomes good linear relationship with water sample ammonium chloride concentration (or ammonia nitrogen concentration), and this empirical curve can be used as normal data database data.When testing ammonia nitrogen concentration of water sample to be analyzed, the absorbance of synchronization t collected and the normal data of Fig. 4 being made comparisons, the ammonia nitrogen concentration in water sample to be measured can be known.
Data in above-described embodiment obtain by adopting the examination of automatic fluid injection side.Except automatic fluid injection mode, miniaturized optical formula Water quality ammonia nitrogen pick-up unit of the present invention also can adopt manual fluid injection mode to measure.When adopting manual fluid injection mode, the peristaltic pump in device and four-way valve assembly are replaced by a micro air pump, and utilize ordinary syringe to complete fluid injection.Fig. 5 is the curve over time of the absorbance under variable concentrations aqueous ammonium chloride solution utilizing miniaturized optical formula Water quality ammonia nitrogen pick-up unit of the present invention to record under manual fluid injection mode.The aqueous ammonium chloride solution sample volume injected in tank in this twice test identical (4 milliliters), but concentration difference (is 1 mg/litre, and another is 2 mg/litre).The adding liquid sum concentration injected is identical, the NaOH aqueous solution of 1.5 mol/L that to be all 1 ml concn be.As can be seen from Figure 5 increase along with the increase of ammonium chloride concentration in phase absorbance in the same time.Test the change curve in time of the absorbance corresponding to aqueous ammonium chloride solution sample of other concentration under the same conditions, production standard database thus.Then the water sample to be measured of the unknown is tested, and the data in test result and standard database are compared, obtain ammonia nitrogen concentration or the content of water sample to be measured thus.
A kind of miniaturization Water quality ammonia nitrogen pick-up unit of the present invention, structure is simple, makes easily, easy and simple to handle, volume is little, lightweight, be easy to carry, highly sensitive, broad quantum, detection limit is low, antijamming capability is strong, water sample does not need pre-service, and ammonia sensitive element is reusable, is suitable for carrying out field quick detection to the ammonia-nitrogen content of the water environments such as river, lake, reservoir, plant chimney stalk, sanitary sewage, water station, water treatment plant.Known to investigating according to us, a kind of miniaturization Water quality ammonia nitrogen pick-up unit of the present invention, not yet reports at present.
Claims (13)
1. a miniaturized optical formula Water quality ammonia nitrogen pick-up unit, is characterized in that, comprises a gas-liquid separation unit, an optical detection unit, a signal processing chip; Wherein:
Gas-liquid separation unit comprises a bowl-shape tank, a groove lid, a peristaltic pump, a four-way valve and connecting duct; The Single port of peristaltic pump is through the first connecting duct connection water channel, and another port second connecting duct connects four-way valve Single port;
Optical detection unit comprises an air chamber, at least one light source, at least one photo-detector, at least one ammonia sensitive element; Light source is positioned at air chamber madial wall, and photo-detector is positioned at another madial wall of air chamber, just right with light source; Ammonia sensitive element is positioned in the middle of light source and photo-detector, and upper end is fixed in air chamber inner roof wall, in the light path of light source, light source light is vertically received by photo-detector through after ammonia sensitive element;
Tank under, air chamber upper, tank opening seals with air chamber opening and docks, and by-level sets firmly groove lid, and groove covers and is provided with multiple micro-through-hole, makes the gas of the gentle indoor of tank can phase counterdiffusion;
Another three ports connection air chamber of four-way valve, one connects catheter, and one is unsettled for subsequent use; The catheter other end and water sample to be measured or annex solution container interlink, for water sample to be measured or annex solution are injected, discharge tank;
Tank diapire has a through hole, one end of through hole and the first connecting duct is tightly connected, and the other end and the peristaltic pump Single port of the first connecting duct are tightly connected, and peristaltic pump another port second connecting duct and four-way valve Single port are tightly connected;
Photo-detector exports and is electrically connected with outside signal processing chip input end, and signal processing chip output terminal is electrically connected on follow-up equipment.
2. miniaturized optical formula Water quality ammonia nitrogen pick-up unit as claimed in claim 1, it is characterized in that, described air chamber is made up of metal or black plastic light-proof material; Tank, groove lid and four-way valve are made up of organic glass or teflon alkali resistant materials; Wherein, groove lid uses light-proof material.
3. miniaturized optical formula Water quality ammonia nitrogen pick-up unit as claimed in claim 1, it is characterized in that, described ammonia sensitive element, comprise light tight fixture or printing opacity and meet the sensitive diaphragm of ammonia generation color change, two jig arm centers of light tight fixture respectively have a through hole, two through hole is relative, and ammonia sensitive diaphragm is entirely placed in two jig arm intermediate groove, and covers the through hole in two jig arm completely;
The through hole that light tight fixture two jig arm is opened, respectively just to light source, photo-detector, makes light source light pass after ammonia sensitive diaphragm through relative through hole, is radiated at photo-detector receiving end.
4. the miniaturized optical formula Water quality ammonia nitrogen pick-up unit as described in claim 1 or 3, it is characterized in that, described ammonia sensitive diaphragm, for porous structure, make of fritted glass, porous filter paper or porous polymer, have in hole and can react the chemical substance of variable color at normal temperatures and pressures with ammonia: polyaniline, thymol blue or bromthymol blue.
5. miniaturized optical formula Water quality ammonia nitrogen pick-up unit as claimed in claim 1, is characterized in that, described annex solution, for concentration is not less than NaOH or the KOH aqueous solution of 1 mol/L.
6. the miniaturized optical formula Water quality ammonia nitrogen pick-up unit as described in claim 1 or 3, it is characterized in that, described air chamber inner roof wall has a through hole, through hole is tightly connected through the 3rd connecting duct and four-way valve Single port, makes the air in air chamber back and forth be pumped in tank by four-way valve and peristaltic pump; Air chamber madial wall is provided with groove, and with fixed light source, photo-detector, electrical connection place that light source and photo-detector pass air chamber wall seals with glue; Air chamber inner roof wall is provided with holder, and it is affixed that the light tight fixture upper end of ammonia sensitive element is arranged in holder, and ammonia sensitive element vertically downward, is positioned in the light path of light source.
7. miniaturized optical formula Water quality ammonia nitrogen pick-up unit as claimed in claim 1, it is characterized in that, described peristaltic pump is two-way peristaltic pump.
8. miniaturized optical formula Water quality ammonia nitrogen pick-up unit as claimed in claim 1, is characterized in that, described catheter, for silicon rubber or polytetrafluoroethylmaterial material make, for injecting and discharging water sample to be measured or annex solution; Regulate four-way valve after opening peristaltic pump; When rotating forward, water sample to be measured or annex solution can be injected into tank; During reversion, peristaltic pump makes water sample to be measured or annex solution discharge tank.
9. miniaturized optical formula Water quality ammonia nitrogen pick-up unit as claimed in claim 1, is characterized in that, described light source, the absorption spectrum ranges that its emission wavelength produces after being positioned at the variable color of ammonia sensitive element; Photo-detector, be the light activated photodiode that sends light source or photoelectric cell, the output electric signal of this detector is linear with the light intensity be radiated on photo-detector.
10. miniaturized optical formula Water quality ammonia nitrogen pick-up unit as claimed in claim 1, it is characterized in that, in same air chamber, arrange an optical detecting channel and an optics reference channel, optical detecting channel is made up of a light source, a photo-detector and an ammonia sensitive element; Optics reference channel is made up of a light source, a photo-detector and a reference elements; Reference elements is identical with ammonia sensitive element structure, do not add in the perforated membrane film perforation that difference is only reference elements fill can with the perforated membrane film perforation of the chemical substance of ammonia gas react variable color and sensitive element in add be filled with can with the chemical substance of ammonia gas react variable color; Difference measurement is carried out to the photodetector output signal of optics reference channel and the photodetector output signal of optical detecting channel.
11. miniaturized optical formula Water quality ammonia nitrogen pick-up units as claimed in claim 1, it is characterized in that, in same air chamber, multiple light source, multiple photo-detector, multiple ammonia sensitive element are set, each light source, a photo-detector, an ammonia sensitive element form an optical detecting channel, form multiple optical detecting channel thus, sensitive diaphragm thickness in the ammonia sensitive element of each sense channel is different, expand pick-up unit thus to the measurement range of Water quality ammonia nitrogen, realize many precision, multirange detects.
12. miniaturized optical formula Water quality ammonia nitrogen pick-up units as claimed in claim 1, is characterized in that, described peristaltic pump and four-way valve are manually got available micro air pump liquid replaces automatically getting liquid in employing and replaced; Micro air pump air intake opening is tightly connected through the first connecting duct and air chamber inner roof wall through hole, micro air pump gas outlet be tightly connected through the 3rd connecting duct and tank diapire through hole; Air in air chamber is back and forth pumped in tank by micro air pump; Manually getting liquid uses syringe to complete, during fluid injection, first connecting duct is separated with air chamber inner roof wall through hole, then water sample to be measured or annex solution are injected in tank through air chamber inner roof wall through hole and groove lid micropore by syringe needle, remove needle and syringe head fast afterwards and the first connecting duct and air chamber inner roof wall through hole are tightly connected.
The detection method of 13. 1 kinds of miniaturized optical formula Water quality ammonia nitrogen pick-up units as claimed in claim 1, it is characterized in that, flow process is:
Steps A) make the standard database of ammonia nitrogen concentration;
Step B) regulate four-way valve, open peristaltic pump and rotate forward, in tank, pump into the water sample to be measured that a volume is 1 to 8 milliliter, then switch four-way valve and make gas in air chamber pump into tank;
Step C) power to photo-detector, signal processing chip and follow-up equipment, the background signal of harvester before opening light source;
Step D) open light source, and monitor light source light through the light intensity change after ammonia sensitive element until photodetector output signal changes no longer in time;
Step e) switch four-way valve and volume is 1 to 5 milliliter and the annex solution that concentration is not less than the NaOH aqueous solution of 1 mol/L pumps into tank, the pH value of liquid in tank is made to be greater than 11, and then switching four-way valve makes gas in air chamber pump into tank, continuous acquisition photodetector output signal simultaneously;
Step F) stop test when observing after photodetector signal changes no longer in time, then switch four-way valve and make peristaltic pump reverse rotation to discharge the liquid in tank;
Step G) after the liquid in tank is thoroughly discharged, switch four-way valve and under peristaltic pump drives, enter air chamber from the pore of air chamber by outside air, ammonia sensitive element is replied, or separated gas chamber and tank, allow ammonia sensitive element be exposed in air automatically reply, to use next time;
Step H) result recorded is carried out processing after and steps A) the normal data database data that makes compares, to obtain the ammonia nitrogen concentration in water sample to be measured.
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