CN103439258B - A kind of water nutrition in situ detection instrument based on integrated valve terminal device and detection method - Google Patents

A kind of water nutrition in situ detection instrument based on integrated valve terminal device and detection method Download PDF

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CN103439258B
CN103439258B CN201310407570.8A CN201310407570A CN103439258B CN 103439258 B CN103439258 B CN 103439258B CN 201310407570 A CN201310407570 A CN 201310407570A CN 103439258 B CN103439258 B CN 103439258B
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cover plate
sample
solenoid valve
water
base plate
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CN103439258A (en
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王洪亮
张述伟
褚东志
马然
郭翠莲
王昭玉
程岩
侯广利
刘岩
王茜
石小梅
刘东彦
任国兴
吕婧
曹璐
范萍萍
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Oceanographic Instrumentation Research Institute Shandong Academy of Sciences
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Oceanographic Instrumentation Research Institute Shandong Academy of Sciences
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Abstract

The invention discloses a kind of water nutrition in situ detection instrument based on integrated valve terminal device and detection method, it comprises integrated valve terminal, peristaltic pump, well heater, optical flow cell, LED, photoelectricity acquisition module, computer processing module, present invention also offers and utilize described nutrients in sea water in situ detection instrument to carry out the method for on-line checkingi nutrients in sea water, nutritive salt automatic tester of the present invention is based on integrated valve terminal device, valve island device completes selectivity sample introduction, mixing, integrated level is high, volume is little, is adapted at line analysis; Can complete the mensuration of multiple nutrients salt under single peristaltic pump drives, energy consumption is low, is conveniently used in home position sensing; The present invention, by T-valve and parallel heating reaction coil pipe, reduces external environmental condition to the impact of measurement result, increases temperature of reaction, chemical colour reaction time, thus increase reaction process, increase the sensitivity analyzed.

Description

A kind of water nutrition in situ detection instrument based on integrated valve terminal device and detection method
Technical field
The invention belongs to sewater chemistry analysis field, be specifically related to a kind of water nutrition in situ detection instrument based on integrated valve terminal device and detection method.
Background technology
Nutritive salt is the necessary nutrient of phytoplankton growth in water body, is one of important parameter of ecological monitoring.The change of monitoring nutrient salt in water concentration, has great importance for monitoring water pollution, the circulation of research marine geochemistry, early warning ecocatas-trophe etc.At present, seawater Middle nutrition salt measures mainly according to marine monitoring specification (GB17378 2007), adopts the spot sampling laboratory method based on research ship.The method has poor real, sample vulnerable to pollution, the drawback such as waste of manpower, material resources.In recent years, one of the development study hotspot becoming marine field of ocean original position nutritive salt sensor.Ocean original position nutritive salt sensor is based on microscale experiment room technology and spectrophotometric method, measure and determine the content of its nutritive salt according to the change of seawater sample absorbance, possessing that energy consumption is low, volume is little, reagent dosage is few, stable performance, automaticity high.
Fluid and chromogenic reaction control device, the flow velocity of Control Assay, reagent, flow and entering order, controlling the mixing of reagent and sample, reaction and colour developing, is the core component of ocean original position nutritive salt sensor.Existing nutrients in sea water analytical instrument many employings one-parameter Single channel analysis, its fluid and chromogenic reaction control device mostly are single channel distributed structure, the corresponding passage of each nutritive salt parameter, each passage all needs fluid control device, mixing reactor, peristaltic pump, automatic sampling valve and optical flow cell, complex structure, there are the deficiencies such as integrated level is low, volume is large, energy consumption is high, reagent dosage is large, should not in site measurement be used in.
Summary of the invention
The present invention is directed to the deficiency that prior art exists, provide a kind of water nutrition in situ detection instrument based on integrated valve terminal device and detection method.It can overcome existing fluid and the deficiency existing for chromogenic reaction control device, reduces energy consumption, reduced volume, reduction reagent dosage, improves integrated level, be used in home position sensing easily.
For achieving the above object, the present invention adopts following technical proposals to be achieved:
Based on a water nutrition in situ detection instrument for integrated valve terminal device, it comprises integrated valve terminal, peristaltic pump, well heater, optical flow cell, LED, photoelectricity acquisition module, computer processing module,
Described integrated valve terminal comprises cover plate assembly and bottom deck assembly, described cover plate assembly comprises the web member of cover plate matrix and hollow, described cover plate matrix is provided with internal channel, described web member inserts described internal channel and is fixedly connected with cover plate matrix, in described web member, vacancy is provided with liquid delivery tube, and described liquid delivery tube is communicated with internal channel;
Described bottom deck assembly comprises base plate matrix and multiple in solenoid valve in parallel, solenoid valve to be fixed on base plate matrix and and in sealing between base plate matrix, described base plate matrix is provided with the base plate drainage through hole for connected electromagnetic valve and internal channel;
Described cover plate matrix is fixedly connected with between base plate matrix, and the electromagnetic valve outlet of described integrated valve terminal is connected with peristaltic pump entrance, and wriggling delivery side of pump is connected with well heater, and well heater is connected with optical flow cell, photoelectricity acquisition module and computer processing module successively.
Further, described internal channel comprises the cover plate upper end through hole and microchannel, cover plate lower end that are interconnected.
Further, described liquid delivery tube is connected with the entrance of described solenoid valve with cover plate upper end through hole, microchannel, cover plate lower end, base plate drainage through hole successively.
Further, described liquid delivery tube is polyfluortetraethylene pipe, and the web member through hollow is through with internal channel, base plate drainage through hole, solenoid valve successively.
Further, described web member is the nut of hollow, and described nut has external thread, and described cover plate matrix is provided with the internal thread adapted to external thread.
Further, described cover plate upper end through hole is 6-60, and microchannel, cover plate lower end is 4-40, and internal diameter is 0.5mm-2mm.
Further, described base plate drainage through hole internal diameter is 0.5mm-2mm, and described polyfluortetraethylene pipe external diameter is 1mm-4mm, internal diameter is 0.5mm-2mm, and described nut inner hole footpath is 1mm-4mm.
Present invention also offers the method for the water nutrition in situ detection instrument on-line checkingi nutrient salt in water concentration described in utilization, it comprises the following steps:
Open peristaltic pump, pump into sample to be detected by solenoid valve; Developer is pumped into again respectively to reacting stream and being mixed to form mixed liquor with the sample S-phase in stream by solenoid valve; Then by well heater, mixed solution heating is promoted that mixed solution reacts and develops the color; Open LED, the solution after colour developing enters optical flow cell and obtains light intensity I through photoelectricity acquisition module, computer processing module,
Opens solenoid valve, pumps into distilled water; Open LED, distilled water enters optical flow cell and obtains light intensity I through photoelectricity acquisition module, computer processing module 0, utilize formula try to achieve sample absorbance to be detected,
According to the regression equation of the absorbance-concentration working curve of the standard specimen of a series of concentration known, calculate the content of the nutrients in sea water in sample.
Wherein, when sample to be detected is for containing NO 2during-N solution, nitrite ion used is sulfanilamide (SN)-aqueous hydrochloric acid solution and hydrochloride naphthodiamide aqueous solution, and described sulfanilamide (SN)-aqueous hydrochloric acid solution consists of: the mass percent of sulfanilamide (SN) is 1 ~ 4%, and the concentration of hydrochloric acid is 1mol/L ~ 2mol/L; Described hydrochloride naphthodiamide aqueous solution consists of: the mass percent of hydrochloride naphthodiamide is 0.2 ~ 0.5%.
Wherein, when sample to be detected is for containing PO 4during-P solution, nitrite ion used is for being ammonium molybdate-potassium antimony tartrate-aqueous sulfuric acid and aqueous ascorbic acid, described ammonium molybdate-potassium antimony tartrate-aqueous sulfuric acid consists of: the mass percent of ammonium molybdate is 0.5 ~ 2%, the mass percent of potassium antimony tartrate is 0.02 ~ 0.1%, and the concentration of sulfuric acid is 1mol/L ~ 3mol/L; Described aqueous ascorbic acid consists of: the mass percent of ascorbic acid is 1 ~ 3%.
Compared with prior art, advantage of the present invention and good effect are:
1, nutrient salt automatic analyser of the present invention is based on integrated valve terminal device, and valve island device completes selectivity sample introduction, mixing, and integrated level is high, volume is little, is adapted at line analysis.
2, nutrient salt automatic analyser of the present invention completes the mensuration of multiple nutrients salt under single peristaltic pump drives, and energy consumption is low, is conveniently used in home position sensing.
3, nutritive salt automatic analysis method of the present invention is when continuous sample introduction, by T-valve and parallel heating reaction coil pipe, reduce external environmental condition to the impact of measurement result, increase temperature of reaction, chemical colour reaction time, increase reaction process, thus increase the sensitivity analyzed.
After reading the specific embodiment of the present invention by reference to the accompanying drawings, the other features and advantages of the invention will become clearly.
Accompanying drawing explanation
Fig. 1 is the structural representation of integrated valve terminal device of the present invention, in figure, and 1-cover plate matrix; The hand-tight nut of 2-; 3-hermetic collar; 4-O-ring seal; 5-polyfluortetraethylene pipe; 6-base plate matrix; 7-solenoid valve; 8-fixed screw; 9-O-ring seal; A1-fixing threaded hole; A2-through hole internal thread; A3-cover plate upper end through hole; Microchannel, A4-cover plate lower end; B1-fixing threaded hole; B2-fixing threaded hole; B3-base plate drainage through hole.
Fig. 2 is the structural representation of nutrients in sea water in situ detection instrument of the present invention, is also the process chart of multiple nutrients salt automatic analysis method of the present invention, in figure, and V1-first three-way solenoid valve; V2-second three-way solenoid valve; V3-the 3rd three-way solenoid valve 3; V4-the 4th three-way solenoid valve; V5-the 5th three-way solenoid valve; V6-the 6th three-way solenoid valve 6; R1-first developer; R2-second developer; R3-the 3rd developer; R4-the 4th developer; S-sample; DIW-distilled water; WW-waste liquid; 10-peristaltic pump; 11A-heating coil; 11B-heating coil; The threeway of 12-T type; 13-optical flow cell; 14-photoelectricity acquisition module; 15-computer processing module.
Embodiment
Below by embodiment, the structure of the nutrients in sea water in situ detection instrument based on integrated valve terminal device of the present invention and the operation of multiple nutrients salt automatic analysis method of the present invention are explained further.
Embodiment 1
The structural representation of multiple nutrients salt automatic analyzer as shown in Figure 1, comprises integrated valve terminal, peristaltic pump 10, well heater (in the present embodiment, well heater is heating coil 11A and heating coil 11B), T-shaped threeway 12, optical flow cell 13, photoelectricity acquisition module 14 and computer processing module 15.Described sample to be tested, distilled water, multiple developer, by three-way solenoid valve in control integration valve island, realize the selectivity sample introduction of nutritive salt sample and developer and mix.
In the present embodiment, the structure of integrated valve terminal device as shown in Figure 1, comprises cover plate assembly and bottom deck assembly, the fluid intake of the integrated multiple solenoid valve of integrated valve terminal, sample to be tested, distilled water, multiple developer and outlet.
Described cover plate assembly comprises the web member of cover plate matrix 1 and hollow, also comprises seal member: hermetic collar 3 and O-ring seal 4.In the present embodiment, the web member of hollow is the hand-tight nut 2 of hollow, and described cover plate matrix 1 is provided with internal channel and through hole internal thread A2, and described hand-tight nut 2 has external thread, and is fixed on cover plate matrix 1 by through hole internal thread A2.Described internal channel can be straight channel, can be comprise the cover plate upper end through hole A3 and cover plate lower end microchannel A4 that are interconnected, described cover plate matrix 1 upper surface is provided with cover plate fixing threaded hole A1, corresponding with the base plate fixing threaded hole B1 that base plate is provided with, for connecting cover plate, base plate.
The intermediate throughholes place of described hand-tight nut 2 is provided with liquid delivery tube, and in the present embodiment, liquid delivery tube is polyfluortetraethylene pipe 5, the internal diameter of the intermediate throughholes of hand-tight nut 2 and the external diameter of polyfluortetraethylene pipe 5 close, for through polyfluortetraethylene pipe.Described hand-tight nut 2 port is back taper, and its pyramidal structure and the positive taper structure matching of hermetic collar 3 seal for realizing.The external diameter of described hermetic collar 3 endoporus and polyfluortetraethylene pipe 5 is close.Described polyfluortetraethylene pipe 5, through vacancy, hermetic collar 3 through hole in hand-tight nut 2, is fixed on cover plate matrix 1 internal channel end face by hand-tight nut 2 external thread, hermetic collar 3, O-ring seal 4, through hole internal thread A2.Described polyfluortetraethylene pipe 5 is connected with cover plate lower end microchannel A4 by cover plate upper end through hole A3.Described polyfluortetraethylene pipe 5, for introducing fluid to cover plate inlet end, is drawn by cover plate endpiece, be can be used as fluid intake and fluid outlet after cover plate lower surface microchannel, base plate drainage through hole.Described polyfluortetraethylene pipe 5 internal diameter is identical or close with the diameter of cover plate upper end through hole A3, cover plate lower end microchannel A4.Enter caliber before and after valve plate due to fluid and geometric configuration does not have a greater change, fluid can keep original flow velocity and laminar condition in internal channel, does not produce larger diffusion, thus affects measurement sensistivity.
Described bottom deck assembly comprises base plate matrix 6, solenoid valve 7, fixed screw 8, O-ring seal 9.Described base plate matrix 6 upper surface contains fixing threaded hole B1, corresponding with cover plate fixing threaded hole A1, for connecting cover plate, base plate.Described base plate matrix 6 comprises fixing threaded hole B2 and base plate drainage through hole B3, described fixing threaded hole B2 are used for Motionless electromagnetic valve, and described base plate drainage through hole B3 is used for connected electromagnetic valve aperture and cover plate upper end through hole A3, cover plate lower end microchannel A4.
Described solenoid valve 7 material is PEEK, can prevent the erosion of the solution such as acid, alkali, high salt.Described solenoid valve 7 is fixed on base plate matrix 6 by fixed screw 8, fixing threaded hole B2 and O-ring seal 9.Fluid, under the driving of peristaltic pump 10, through polyfluortetraethylene pipe 5, cover plate upper end through hole A3, cover plate lower end microchannel A4, base plate drainage through hole B3, enters solenoid valve 7.Described solenoid valve 7 is commercially available two-position three way magnetic valve, has three apertures, working pressure 2 ~ 3 × 10 5pa.Three apertures are respectively as two imports of fluid and an outlet.When solenoid valve power-off, normal port is connected with outlet, and fluid is entered by normal open mouth, and electromagnetic valve outlet flows out; When solenoid valves, normally closed port is connected with outlet, and fluid is entered by normally closed port, and electromagnetic valve outlet flows out, thus the selectivity controlling fluid flows into.Described three-way solenoid valve aperture is connected with cover plate upper end through hole A3, cover plate lower end microchannel A4 by base plate drainage through hole B3.Described multiple solenoid valve is in parallel, and solenoid control drainage body water route can be connected in series or in parallel.
Described sample to be tested, distilled water, multiple developer, by switch and the working time of three-way solenoid valve in control integration valve island, thus the selectivity sample introduction of control fluid, Loading sequence and sample size; By controlling the switch of peristaltic pump, pump speed and reversion, thus control sample introduction speed, the sample mixed of fluid; By controlling Loading sequence, sample size, the sample introduction speed of water body and reaction reagent, realize mixing of nutritive salt sample and developer.Mixed solution, through polyfluortetraethylene pipe 5, peristaltic pump 10, solenoid valve V6, is transported to heating coil 11 and reacts, develops the color.Described heating coil controls heating-up temperature by control circuit.
Solution to be measured after colour developing arrives optical flow cell 13 through T-shaped threeway 12.Described optical flow cell 13 is Z-type flow cell, is provided with fluid intake, fluid egress point and light entrance port, optical emission exit.Light source is the LED of specific wavelength, after coupling, enter light entrance port by fiber optic conduction.Open the LED of specific wavelength, solution to be measured, after fluid intake enters, after LED is irradiated, is flowed out by fluid egress point.The light of described specific wavelength utilizes photoelectricity acquisition module 14 to gather light signal and utilizes computer processing module 15 to calculate the absorbance of the rear solution of colour developing.Calculate the concentration of nutritive salt according to the absorbance of typical curve and chromophoric solution, finally realize the mensuration of nutrients in sea water content.
In situ detection instrument provided by the invention, described cover plate fixing threaded hole A1, base plate fixing threaded hole B1 are 4-32.Described cover plate upper end through hole A3 is 6-60, and cover plate lower end microchannel A4 is 4-40, and internal diameter is 0.5mm-2mm.Described base plate conduction hole internal diameter is 0.5mm-2mm.Described polyfluortetraethylene pipe 5 external diameter be 1mm-4mm, internal diameter is 0.5mm-2mm.Described hand-tight nut 2 endoporus, hermetic collar 3 internal diameter are 1mm-4mm.Described peristaltic pump is commercially available 6 rotor pulse pumps, pump discharge 0.4 ~ 24ml/min.Described optical flow cell 13 is Z-type flow cell, is provided with fluid intake, fluid egress point and light entrance port, optical emission exit.
Described cover plate matrix and base plate matrix are organic glass, POM or PEEK, can improve the corrosivity of the chemical reagent such as resistance to strong acid, highly basic, high salt.The mode sealing-ins such as cover plate is successively cohered by organic reagents such as methenyl choloride, acetone, acetic acid with base plate, hot pressing are connected with mechanical anchoring methods.
As shown in Figure 2, in the present embodiment, in integrated valve terminal, be provided with 6 solenoid valves, be respectively the first three-way solenoid valve V1; Second three-way solenoid valve V2; 3rd three-way solenoid valve V3; 4th three-way solenoid valve V4; 5th three-way solenoid valve V5; 6th three-way solenoid valve V6.The normal opening of described first three-way solenoid valve V1 is used for sample S sample introduction, and normally closed port is used for distilled water DIW sample introduction, and outlet is connected with the normal opening of the second three-way solenoid valve V2.Second three-way solenoid valve V2 normally closed port is used for the first developer R1 sample introduction, and outlet is connected with the normal opening of the 3rd three-way solenoid valve V3.3rd three-way solenoid valve V3 normally closed port is used for the second developer R2 sample introduction, and outlet is connected with the normal opening of the 4th three-way solenoid valve V4.4th three-way solenoid valve V4 normally closed port is used for the 3rd developer R3 sample introduction, and outlet is connected with the normal opening of the 5th three-way solenoid valve V5.5th three-way solenoid valve V5 normally closed port is used for the 4th developer R4 sample introduction, exports and is connected with peristaltic pump 10 injection port by polyfluortetraethylene pipe 5.Peristaltic pump 10 outlet exports with the 6th three-way solenoid valve V6 and is connected.The normal opening of 6th three-way solenoid valve V6, normally closed port are connected with heating coil 11A, 11B respectively by polyfluortetraethylene pipe 5.Heating coil 11A, 11B connect and are connected with optical flow cell 13 through T-shaped threeway 12.Optical flow cell outlet is for discharging waste liquid W W.Optical flow cell is connected with photoelectricity acquisition module 14, computer processing module 15 by optical fiber, data line.
Embodiment 2: analyze NO 2-N
The automatic analysis method of multiple nutrients salt of the present invention, uses the automatic analyzer of said structure, can analyze multiple nutrients salt.The present embodiment is with one-parameter NO 2-N example analyzes the NO in seawater, estuarine water and industrial sewage 2-N, the light path of optical flow cell 13 is 20mm, and determined wavelength is 530nm.Its analytical procedure is as follows respectively:
The operation steps of the present embodiment test analysis:
1, the standard specimen needed for test analysis and solution is prepared
(1) standard specimen is prepared
Take NaNO 2(analyzing pure) preparation 1000mg/LNO 2the Standard Reserving Solution of-N, by the Standard Reserving Solution dilution prepared, is mixed with a series of standard specimen, each standard specimen NO 2-N concentration is respectively 5.0 μ g/L, 10.0 μ g/L, 20.0 μ g/L, 40.0 μ g/L and 80.0 μ g/L.
(2) nitrite ion R1 is prepared
Taking 10.0 grams of sulfanilamide (SN) is dissolved in 250mL distilled water, places 5 minutes, then adds the concentrated hydrochloric acid of 75mL, be settled to 500mL after cooling with distilled water.Wherein, the mass percent of sulfanilamide (SN) is the concentration of 2%, HCl is 1.8mol/L.
(3) nitrite ion R2 is prepared
Take 1.5 grams of hydrochloride naphthodiamides to be dissolved in 500mL distilled water.Wherein, the mass percent of hydrochloride naphthodiamide is 0.3%.
2, testing and drawing working curve
Open peristaltic pump, pump into NO 2-N standard specimen S; Opens solenoid valve V2, pumps into the first developer R1 to reacting stream and being mixed to form mixed liquor with the sample S-phase in stream; Shut electromagnetic valve V2, opens solenoid valve V3, pump into the second developer R2 to reacting stream and mixing with the first developer, sample S; Shut electromagnetic valve V3, pumps into mixed solution to heating coil 11A; Heating heating coil to 50 DEG C, promotes mixed solution colour developing; Open 530nmLED lamp, the solution after colour developing enters optical flow cell and obtains 530nm place light intensity I through photoelectricity acquisition module, computer processing module, closes 530nmLED lamp.Opens solenoid valve V1, pumps into distilled water DIW; Open 530nmLED lamp, distilled water enters optical flow cell and obtains 530nm place light intensity I through photoelectricity acquisition module, computer processing module 0, close 530nmLED lamp.Utilize formula try to achieve sample absorbance.
Use the NO of a series of concentration known 2-N standard specimen replaces sample S, repeats above-mentioned steps, obtains absorbance-concentration working curve; The regression equation of working curve and sample absorbance is utilized to calculate NO in sample 2-N content.
Prepared standard specimen is analyzed to high concentration successively by low concentration, obtain a series of standard specimen spectrogram, with the absorbance of standard specimen (A) for ordinate, with the concentration of standard specimen (μ g/L) for horizontal ordinate, can working curve be drawn out, and obtain the regression equation of working curve.
3, sample testing result calculates
Test sample S, obtains the absorbance of sample, and then can calculate the NO in sample by the regression equation of described working curve 2-N content.
Embodiment 3: analyze PO 4-P
The present embodiment analyzes the PO in seawater, estuarine water and industrial sewage 4-P, use the automatic analyzer described in embodiment 1, the light path of optical flow cell 13 is 20mm, and determined wavelength is 880nm.
The operation steps of the present embodiment test analysis:
1, the standard specimen needed for test analysis and solution is prepared
(1) standard specimen is prepared
Take KH 2pO 4(analyzing pure) preparation 1000mg/LPO 4the Standard Reserving Solution of-P, by the Standard Reserving Solution dilution prepared, is mixed with a series of standard specimen, each standard specimen PO 4-P concentration is respectively 5.0 μ g/L, 10.0 μ g/L, 20.0 μ g/L, 40.0 μ g/L and 80.0 μ g/L.
(2) nitrite ion R3 is prepared
A () takes 10.0g ammonium molybdate and is dissolved in 400mL distilled water;
B (), in plastic containers, adds about 200mL distilled water, injected while stirring by the 110mL concentrated sulphuric acid, after cooling, adds water to and is settled to 500mL;
C () takes 0.5 gram of potassium antimony tartrate in 100mL distilled water;
First (a) slowly injected (b) and stir, then adding (c) and fully mix.Wherein, the mass percent of ammonium molybdate is 1%, and the mass percent of potassium antimony tartrate is 0.05%, and the concentration of sulfuric acid is 2mol/L.
(3) nitrite ion R4 is prepared
Take 10.0g ascorbic acid to be dissolved in 500mL distilled water.This solution should be colourless, but slowly oxidation can become filbert after the week, loses effect gradually.Wherein, the mass percent of ascorbic acid is 2%.
2, testing and drawing working curve
Open peristaltic pump, pump into PO 4-P standard specimen S; Opens solenoid valve V4, pumps into the first developer R3 to reacting stream and being mixed to form mixed liquor with the sample S-phase in stream; Shut electromagnetic valve V4, opens solenoid valve V5, pump into the second developer R4 to reacting stream and mixing with the first developer, sample S; Shut electromagnetic valve V5, pumps into mixed solution to heating coil 11A; Heating heating coil to 50 DEG C, promotes mixed solution colour developing; Open 880nmLED lamp, the solution after colour developing enters optical flow cell and obtains 880nm place light intensity I through photoelectricity acquisition module, computer processing module, closes 880nmLED lamp.Opens solenoid valve V1, pumps into distilled water DIW; Open 880nmLED lamp, distilled water enters optical flow cell and obtains 880nm place light intensity I through photoelectricity acquisition module, computer processing module 0, close 880nmLED lamp.Utilize formula try to achieve sample absorbance.
Use the PO of a series of concentration known 4-P standard specimen replaces sample S, repeats above-mentioned steps, obtains absorbance-concentration working curve; The regression equation of working curve and sample absorbance is utilized to calculate PO in sample 4-P content.
Prepared standard specimen is analyzed to high concentration successively by low concentration, obtain a series of standard specimen spectrogram, with the absorbance of standard specimen (A) for ordinate, with the concentration of standard specimen (μ g/L) for horizontal ordinate, can working curve be drawn out, and obtain the regression equation of working curve.
3, sample testing result calculates
Test sample S, obtains the absorbance of sample, and then can calculate the PO in sample by the regression equation of described working curve 4-P content.
Embodiment 4: analyze NO 2-N and PO 4-P
The present embodiment analyzes the NO in seawater, estuarine water and industrial sewage 2-N, PO 4-P, use the automatic analyzer described in embodiment 1, the light path of optical flow cell 13 is 20mm, NO 2-N determined wavelength is 880nm.
1, the standard specimen needed for test analysis and solution is prepared
(1) standard specimen is prepared
Take NaNO 2(analyzing pure), KH 2pO 4(analyzing pure) preparation NO 2-N, PO 4-P concentration is the Standard Reserving Solution of 1000mg/L, and by the Standard Reserving Solution dilution prepared, be mixed with a series of standard specimen, each standard specimen is containing NO 2-N, PO 4-P concentration is 5.0 μ g/L, 10.0 μ g/L, 20.0 μ g/L, 40.0 μ g/L and 80.0 μ g/L.
(2) nitrite ion R1 is prepared
Taking 10.0 grams of sulfanilamide (SN) is dissolved in 250mL distilled water, places 5 minutes, then adds the concentrated hydrochloric acid of 75mL, be settled to 500mL after cooling with distilled water.Wherein, the mass percent of sulfanilamide (SN) is the concentration of 2%, HCl is 1.8mol/L.
(3) nitrite ion R2 is prepared
Take 1.5 grams of hydrochloride naphthodiamides to be dissolved in 500mL distilled water.Wherein, the mass percent of hydrochloride naphthodiamide is 0.3%.
(4) nitrite ion R3 is prepared
A () takes 10.0g ammonium molybdate and is dissolved in 400mL distilled water;
B (), in plastic containers, adds about 200mL distilled water, injected while stirring by the 110mL concentrated sulphuric acid, after cooling, adds water to and is settled to 500mL;
C () takes 0.5 gram of potassium antimony tartrate in 100mL distilled water;
First (a) slowly injected (b) and stir, then adding (c) and fully mix.Wherein, the mass percent of ammonium molybdate is 1%, and the mass percent of potassium antimony tartrate is 0.05%, and the concentration of sulfuric acid is 2mol/L.
(5) nitrite ion R4 is prepared
Take 10.0g ascorbic acid to be dissolved in 500mL distilled water.This solution should be colourless, but slowly oxidation can become filbert after the week, loses effect gradually.Wherein, the mass percent of ascorbic acid is 2%.
2, testing and drawing working curve
Open peristaltic pump, pump into NO 2-N, PO 4-P standard specimen S; Opens solenoid valve V2, pumps into the first developer R1 to reacting stream and being mixed to form mixed liquor with the sample S-phase in stream; Shut electromagnetic valve V2, opens solenoid valve V3, pump into the second developer R2 to reacting stream and mixing with the first developer, sample S; Shut electromagnetic valve V3, pumps into mixed solution to heating coil 11A; Heating heating coil 11A to 50 DEG C, promotes mixed solution colour developing.
Opens solenoid valve V6, pumps into sample S; Opens solenoid valve V4, pumps into the first developer R3 to reacting stream and being mixed to form mixed liquor with the sample S-phase in stream; Shut electromagnetic valve V5, opens solenoid valve V4, pump into the second developer R4 to reacting stream and mixing with the first developer, sample S; Shut electromagnetic valve V5, pumps into mixed solution to heating coil 11B; Heating heating coil 11B to 50 DEG C, promotes mixed solution colour developing.
Shut electromagnetic valve V6, open 530nmLED lamp, the solution after colour developing enters optical flow cell and obtains 530nm place light intensity I through photoelectricity acquisition module, computer processing module 1.Opens solenoid valve V6, open 880nmLED lamp, the solution after colour developing enters optical flow cell and obtains 880nm place light intensity I through photoelectricity acquisition module, computer processing module 2.Opens solenoid valve V1, pumps into distilled water DIW; Open 530nmLED lamp, 880nmLED lamp successively, water to be distilled enters optical flow cell and obtains 530nm, 880nm place light intensity I through photoelectricity acquisition module, computer processing module 01, after I02, close 530nm, 880nmLED lamp successively.Utilize formula try to achieve sample absorbance.
Prepared standard specimen is analyzed to high concentration successively by low concentration, obtains a series of standard specimen spectrogram, with the absorbance of standard specimen (A) for ordinate, with the concentration of standard specimen (μ g/L) for horizontal ordinate, NO can be drawn out respectively 2-N, PO 4-P working curve, and the regression equation obtaining working curve.
3, sample testing result calculates
Test sample S, obtains the absorbance of sample, and then can calculate the NO in sample by the regression equation of described working curve 2-N, PO 4-P content.
Use the NO of a series of concentration known 2-N, PO 4-P standard specimen replaces sample S, repeats above-mentioned steps, obtains NO respectively 2-N, PO 4-P absorbance-concentration working curve; The regression equation of working curve and sample absorbance is utilized to calculate NO in sample 2-N, PO 4-P content.
Above embodiment only in order to technical scheme of the present invention to be described, but not is limited; Although with reference to previous embodiment to invention has been detailed description, for the person of ordinary skill of the art, still can modify to the technical scheme described in previous embodiment, or equivalent replacement is carried out to wherein portion of techniques feature; And these amendments or replacement, do not make the essence of appropriate technical solution depart from the spirit and scope of the present invention's technical scheme required for protection.

Claims (10)

1., based on a water nutrition in situ detection instrument for integrated valve terminal device, it is characterized in that it comprises integrated valve terminal, peristaltic pump, well heater, optical flow cell, LED, photoelectricity acquisition module, computer processing module,
Described integrated valve terminal comprises cover plate assembly and bottom deck assembly, described cover plate assembly comprises the web member of cover plate matrix and hollow, described cover plate matrix is provided with internal channel, described web member inserts described internal channel and is fixedly connected with cover plate matrix, in described web member, vacancy is provided with liquid delivery tube, and described liquid delivery tube is communicated with internal channel;
Described bottom deck assembly comprises base plate matrix and multiple in solenoid valve in parallel, solenoid valve to be fixed on base plate matrix and and in sealing between base plate matrix, described base plate matrix is provided with the base plate drainage through hole for connected electromagnetic valve and internal channel;
Described cover plate matrix is fixedly connected with between base plate matrix, and the electromagnetic valve outlet of described integrated valve terminal is connected with peristaltic pump entrance, and wriggling delivery side of pump is connected with well heater, and well heater is connected with optical flow cell, photoelectricity acquisition module and computer processing module successively.
2. the water nutrition in situ detection instrument based on integrated valve terminal device according to claim 1, is characterized in that: described internal channel comprises the cover plate upper end through hole and microchannel, cover plate lower end that are interconnected.
3. the water nutrition in situ detection instrument based on integrated valve terminal device according to claim 2, is characterized in that: described liquid delivery tube is connected with the entrance of described solenoid valve with cover plate upper end through hole, microchannel, cover plate lower end, base plate drainage through hole successively.
4. the water nutrition in situ detection instrument based on integrated valve terminal device according to claim 2, is characterized in that: described liquid delivery tube is polyfluortetraethylene pipe, and the web member through hollow is through with internal channel, base plate drainage through hole, solenoid valve successively.
5. the water nutrition in situ detection instrument based on integrated valve terminal device according to claim 4, it is characterized in that: described web member is the nut of hollow, and described nut has external thread, described cover plate matrix is provided with the internal thread adapted to external thread.
6. the water nutrition in situ detection instrument based on integrated valve terminal device according to claim 2, is characterized in that: described cover plate upper end through hole is 6-60, and microchannel, cover plate lower end is 4-40, and internal diameter is 0.5mm-2mm.
7. the water nutrition in situ detection instrument based on integrated valve terminal device according to claim 5, it is characterized in that: described base plate drainage through hole internal diameter is 0.5mm-2mm, described polyfluortetraethylene pipe external diameter is 1mm-4mm, internal diameter is 0.5mm-2mm, and described nut inner hole footpath is 1mm-4mm.
8. utilize the detection method of the on-line checkingi nutrient salt in water concentration of the water nutrition in situ detection instrument described in any one of claim 1-7, it is characterized in that it comprises the following steps:
Open peristaltic pump, pump into sample to be detected by solenoid valve; Developer is pumped into again respectively to reacting stream and being mixed to form mixed liquor with the sample S-phase in stream by solenoid valve; Then by well heater, mixed solution heating is promoted that mixed solution reacts and develops the color; Open LED, the solution after colour developing enters optical flow cell and obtains light intensity I through photoelectricity acquisition module, computer processing module,
Opens solenoid valve, pumps into distilled water; Open LED, distilled water enters optical flow cell and obtains light intensity I through photoelectricity acquisition module, computer processing module 0, utilize formula to try to achieve sample absorbance to be detected,
According to the regression equation of the absorbance-concentration working curve of the standard specimen of a series of concentration known, calculate the content of the nutrients in sea water in sample.
9. the detection method of on-line checkingi nutrient salt in water concentration according to claim 8, is characterized in that: sample to be detected is for containing NO 2during-N solution, nitrite ion used is sulfanilamide (SN)-aqueous hydrochloric acid solution and hydrochloride naphthodiamide aqueous solution, and described sulfanilamide (SN)-aqueous hydrochloric acid solution consists of: the mass percent of sulfanilamide (SN) is 1 ~ 4%, and the concentration of hydrochloric acid is 1mol/L ~ 2mol/L; Described hydrochloride naphthodiamide aqueous solution consists of: the mass percent of hydrochloride naphthodiamide is 0.2 ~ 0.5%.
10. the detection method of on-line checkingi nutrient salt in water concentration according to claim 8, is characterized in that: sample to be detected is for containing PO 4during-P solution, nitrite ion used is ammonium molybdate-potassium antimony tartrate-aqueous sulfuric acid and aqueous ascorbic acid, described ammonium molybdate-potassium antimony tartrate-aqueous sulfuric acid consists of: the mass percent of ammonium molybdate is 0.5 ~ 2%, the mass percent of potassium antimony tartrate is 0.02 ~ 0.1%, and the concentration of sulfuric acid is 1mol/L ~ 3mol/L; Described aqueous ascorbic acid consists of: the mass percent of ascorbic acid is 1 ~ 3%.
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