CN108181243B - A kind of error reduction method of automatic calibration device of water quality online analyzer - Google Patents
A kind of error reduction method of automatic calibration device of water quality online analyzer Download PDFInfo
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- CN108181243B CN108181243B CN201711220131.0A CN201711220131A CN108181243B CN 108181243 B CN108181243 B CN 108181243B CN 201711220131 A CN201711220131 A CN 201711220131A CN 108181243 B CN108181243 B CN 108181243B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 21
- 230000009467 reduction Effects 0.000 title claims description 6
- 238000002835 absorbance Methods 0.000 claims abstract description 24
- 239000012452 mother liquor Substances 0.000 claims abstract description 18
- 239000000243 solution Substances 0.000 claims description 75
- 238000010790 dilution Methods 0.000 claims description 33
- 239000012895 dilution Substances 0.000 claims description 33
- 238000012937 correction Methods 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 7
- 238000004364 calculation method Methods 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 5
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 3
- 239000003085 diluting agent Substances 0.000 claims 1
- 238000009434 installation Methods 0.000 abstract description 16
- 230000006872 improvement Effects 0.000 abstract description 12
- 238000009826 distribution Methods 0.000 abstract description 11
- 230000009897 systematic effect Effects 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052700 potassium Inorganic materials 0.000 abstract description 4
- 239000011591 potassium Substances 0.000 abstract description 4
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 description 81
- 238000001514 detection method Methods 0.000 description 24
- 238000002156 mixing Methods 0.000 description 23
- 238000003149 assay kit Methods 0.000 description 22
- 239000011259 mixed solution Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 11
- 238000005259 measurement Methods 0.000 description 9
- 238000010586 diagram Methods 0.000 description 8
- 238000006073 displacement reaction Methods 0.000 description 8
- 230000002572 peristaltic effect Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 230000037361 pathway Effects 0.000 description 6
- 239000012086 standard solution Substances 0.000 description 6
- 238000005070 sampling Methods 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000012482 calibration solution Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012795 verification Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000004457 water analysis Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 101000860173 Myxococcus xanthus C-factor Proteins 0.000 description 1
- 101150054854 POU1F1 gene Proteins 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012913 prioritisation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 210000000664 rectum Anatomy 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
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- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Sampling And Sample Adjustment (AREA)
Abstract
The invention discloses a kind of errors of water quality online analyzer self-checking device to reduce method, is c by water quality online analyzer self-checking device compound concentration0Potassium bichromate solution mother liquor measures solution absorbance A under certain wavelength0, solution is prepared under different distribution ratios using calibrating installation, the theoretical absorbance A of solution is calculated using distribution ratios1‑Asi, practical absorbance A is measured under similarity conditionX1‑AXi, according to theoretical absorbance As1‑AsiWith practical absorbance AX1‑AXiObtain the improvement factor K under different distribution ratios1‑Ki, when matching solution, by this improvement factor, play the role of reducing systematic error.
Description
Technical field
The present invention relates to a kind of errors to reduce what error in method more particularly to a kind of Water Test Kits calibrating installation reduced
Reduction method.
Background technique
In environment water monitoring system, generally water body parameter is detected using online water analysis instrument, online water
Whether the detection accuracy of matter analyzer meets national verification regulatory requirements, general to use the manually metering to online water analysis instrument
Performance is calibrated, and the long period (generally requiring 36 hours) of artificial detection in-line analyzer.And water quality on-line analysis
There are certain constant errors for instrument self-checking device itself, and how to reduce constant error is to influence calibrating installation solution
The big research direction prepared.
Summary of the invention
Goal of the invention: in order to overcome the deficiencies in the prior art, the present invention provides one kind, and to can reduce system intrinsic
The error of the water quality online analyzer self-checking device of error reduces method.
Technical solution: to achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of error of water quality online analyzer self-checking device reduces method, comprising the following steps: compound concentration is
c0Potassium bichromate solution mother liquor measures solution absorbance A under certain wavelength0, prepared under different distribution ratios using calibrating installation
Solution calculates the theoretical absorbance A of solution using distribution ratios1-Asi, practical absorbance A is measured under similarity conditionX1-AXi, root
According to theoretical absorbance As1-AsiWith practical absorbance AX1-AXiObtain the improvement factor K under different distribution ratios1-Ki, in proportion solution
When, consider this improvement factor, plays the role of reducing systematic error.
Systematic correction factor KiCalculation formula are as follows:
Ki=Axi/Asi
Wherein, it is managed according to the volume y that the x: the second syringe pump of volume that the first syringe pump draws mother liquor draws dilution
By thinner ratio in(x:y)；Thinner ratio in=x/ (x+y), theoretical absorbance Asi=A0*in, solution theory concentration c after dilutionsi=
c0*in, practical compound concentration cxi=Ki*csi, practical thinner ratio ln=Kiin。
It is preferred: when mother liquid concentration is fixed, and to select specific objective solution concentration ciWhen, first calculate theoretical distribution ratio in, then
Use KiIt is modified, thinner ratio I after amendmentn；Dilution is added when host computer generates first control signal and second control signal
Compare In, change the stepper motor steps of quantitative injection pump to change dv value, In=(x+dv)/(x+dv+y-dv), after correcting at this time
The solution concentration error of preparation reduces systematic error part.
The present invention compared with prior art, has the advantages that
The present invention is fed back by error, so that the solution concentration error prepared after amendment reduces system constant error portion
Point, improve the configuration precision of solution.
Detailed description of the invention
Fig. 1 is the principle of the present invention schematic diagram；
Fig. 2 is workflow schematic diagram of the invention；
Fig. 3 is structural schematic diagram of the invention；
Fig. 4 is the structural schematic diagram of solution mixing pit；
Fig. 5 is the stereoscopic schematic diagram of solution mixing pit；
Fig. 6 is electromagnetism fixed seat structure schematic diagram；
Fig. 7 is slot cover structural schematic diagram；
Fig. 8 is the structural schematic diagram of threeway.
Specific embodiment
In the following with reference to the drawings and specific embodiments, the present invention is furture elucidated, it should be understood that these examples are merely to illustrate this
It invents rather than limits the scope of the invention, after the present invention has been read, those skilled in the art are to of the invention various
The modification of equivalent form falls within the application range as defined in the appended claims.
A kind of error reduction method of water quality online analyzer self-checking device, matches liquid by calibrating installation, through weight chromium
Sour potassium solution absorbance is examined, and solution prepares error and is less than ± 2%, and there are system deviation, at this time repeated property examinations for whole system
It tests when host computer generates first control signal and second control signal, middle introducing system improvement factor K, can reduce mechanical with liquid
Systematic error, so that global error is better than ± 1%.Specific prioritization scheme are as follows:
Compound concentration is c0Potassium bichromate solution mother liquor measures solution absorbance A at 440nm0, existed using calibrating installation
Solution is prepared under different distribution ratios, the theoretical absorbance A of solution is calculated using distribution ratios1-Asi, reality is measured under similarity condition
Border absorbance AX1-AXi, calculate the improvement factor K under different distribution ratios1-Ki, when matching solution, consider this improvement factor, rise
To the effect for reducing systematic error.Improvement factor K stablizes within x months time, can be again after calibrating installation long-play
The absorbance time is carried out, improvement factor is adjusted.
Theoretical thinner ratio in(x:y) refer to that the first syringe pump 4 draws the absorption dilution of the x: the second syringe pump of volume 5 of mother liquor
The volume y of liquid.
Thinner ratio in=x/ (x+y)
Theoretical absorbance Asi=A0*in, solution theory concentration c after dilutionsi=c0*in,
Systematic correction factor Ki=Axi/Asi
Practical compound concentration cxi=Ki*csi
Practical thinner ratio ln=Kiin
Repeated data through test of many times are respectively to KiIt is calculated, when mother liquid concentration is fixed, and selects specific objective
Solution concentration ciWhen, first calculate theoretical distribution ratio in, reuse KiIt is modified, thinner ratio I after amendmentn.The is generated in host computer
Thinner ratio I is added when one control signal and second control signaln, change the stepper motor steps of quantitative injection pump to change dv
Value, In=(x+dv)/(x+dv+y-dv), the solution concentration error prepared after correcting at this time reduce systematic error part.
As shown in figures 1-8, the water quality online analyzer self-checking device that error of the present invention reduces, the water quality are divided online
Analyzer self-checking device includes host computer, the first control module A, the second control module B, third control module C, circuit control
Plate, solution mixing pit 1, mixing pit inlet tube 2, Y-type three way type 3, the first syringe pump 4, the second syringe pump 5, peristaltic pump 6, electromagnetism stir
Mix device 7, detection liquid pipe 8, in which:
The Y-type three way type 3 be two import one outlets pipe fitting, respectively the first inlet tube, the second inlet tube and
First outlet pipe.Described 2 one end of mixing pit inlet tube is connect with first outlet pipe, and the other end is connect with mixing pit.Described first
Liquid check valve 44 and the first inlet tube are sequentially connected out for one end of outlet tube 42, first, and first outlet tube 42 is another
One end is connect with the outlet end of standard mother liquid multi-cavity bottle.One end of second outlet tube 52, second go out liquid check valve 54 and second
Inlet tube is sequentially connected, and the other end of second outlet tube 52 is connect with the outlet end of dilution bottle.
First goes out there are two the purposes that liquid check valve 44 is arranged, and first is to prevent liquid from flowing back from Y-type three way type 3, another
It is, when the first outlet of liquid check valve 44 out less than 4 times first distance L that the closing mouth of liquid check valve 44 is exported to the first inlet tube out
When end pipe diameter r, first, which goes out liquid check valve 44 and the first inlet tube, exports to form turbulence structure, when the first liquid stops to mixing pit
When inlet tube 2 flows into, goes out the closing mouth of liquid check valve 44 first and have the first liquid between the outlet of the first inlet tube, when second
Liquid continues through Y-type three way type 3 and flows into mixing pit inlet tube 2, due to there is folder between the first inlet tube, the second inlet tube
Angle is collided so that rushing at the outlet of the first inlet tube from the second liquid that the second inlet tube flows out with the outlet of the first inlet tube,
Second liquid after collision forms turbulent flow, within and around the outlet of the first inlet tube of agitation, first go out it is molten in liquid check valve 44
Liquid, and then enter first and go out in liquid check valve 44, when turbulent flow to first, which goes out liquid check valve 44, closes mouth, due to closing mouth
Stop, turbulent flow returns, and the solution that first goes out in liquid check valve 44 is taken in the return of turbulent flow out of, and then realizes that first goes out liquid check valve
The exchange of solution in 44 goes out liquid check valve 44 for first and closes mouth to the first liquid having between the outlet of the first inlet tube
It is gradually diluted and is taken out of by the effect of turbulent flow, the influence for avoiding Liquid Residue from preparing solution, and then improve the configuration precision of solution.
Similarly know the second setting purpose for going out liquid check valve 54.
Described first goes out the closing mouth of liquid check valve 44, and to the distance L that the first inlet tube exports, less than 4 times first, liquid is unidirectional out
Valve 44 outlet end caliber r, described second, which goes out liquid check valve 54, closes distance L that mouth is exported to the second inlet tube less than 4 times second
54 outlet end caliber r of liquid check valve out.The distance of the first distance L that the closing mouth of liquid check valve 44 is exported to the first inlet tube out is got over
It is short better, distance it is shorter, turbulent flow is bigger, can preferably contradict second go out liquid check valve 54 close mouth at solution.
As long as Y-type three way type 3 guarantees between the first inlet tube, the second inlet tube that best angle is there are angle
45 °, using PTEF material, the Y-type three way type of special angle make the connecting line in calibrating installation is as short as possible, dead volume as far as possible
It is small.
The mixed solution pond 1 includes with open major trough body 11, slot cover 12, and the slot cover 12 is for covering in major trough body
In 11 opening, major trough body 11 is closed.Star-like handle nut 121 is provided in the slot cover 12.The slot cover 12 and major trough body
The place that 11 opening is in contact is provided with sealing ring.The shape of the inner cavity of the major trough body 11 is infundibulate.The major trough body
11 bottoms are provided with feed pathway 111, detection liquid flow pass 112 and apocenosis passage 113.The apocenosis passage 113 into
Liquid mouth is located at the bottom of 11 inner cavity of major trough body, and the inlet of the feed pathway 111 be higher than detection liquid flow pass 112 into
Liquid mouth, while the inlet of the apocenosis passage 113, lower than the inlet of detection liquid flow pass 112, the detection liquid stream goes out
Channel 112 is for connecting inspection by sampling equipment.
The magnetic stirrer 7 includes electromagnet fixing seat 71, electromagnet 72, stirrer 73, the electromagnet fixing seat
71 for electromagnet 72 to be fixed on to the bottom of major trough body 11, and the stirrer 73 be set to it is intracavitary in major trough body 11.
Fixed block hole 711 is provided in the electromagnet fixing seat 71.Drain pipe passes through fixed block hole 711 and drain
Channel 113 is connected to, and is provided with peristaltic pump 6 on the drain pipe.
The first outlet pipe is connected to by mixing pit inlet tube 2 with the feed pathway 11 in mixed solution pond 1.The mixing
Solution pool 1 includes with open major trough body 11, slot cover 12, and the slot cover 12 is used to cover the opening in major trough body 11, closing
Major trough body 11, star-like handle nut 121 is provided in the slot cover 12, and the place that the slot cover 12 is in contact with opening is provided with
Sealing ring.The shape of the hollow groove of the major trough body 11 is infundibulate, and feed pathway 111, inspection are provided on the major trough body 11
It surveys liquid flow pass 112 and apocenosis passage 113, the inlet of the apocenosis passage 113 is located at the bottom of hollow groove, and it is described
The inlet of feed pathway 111 is higher than the inlet of detection liquid flow pass 112, while the inlet of the apocenosis passage 113
Lower than the inlet of detection liquid flow pass 112, the detection liquid flow pass 112 is used for through detection liquid pipe 8 and water quality point
The connection of analyzer inlet.
The present invention is set to the bottom of hollow groove using feed pathway 111, so that dilution and standard mother liquor are molten from mixing
1 bottom of liquid pool enters mixed solution pond 1, when preventing stirrer 73 from rotating in this way, dilution and standard mother liquor is beaten and fly mixing
On 1 inner wall of solution pool, the mixed-precision of solution is influenced.In addition, stirrer begins to work when having solution in mixed solution pond 1
Make to accelerate mixing velocity to mix test solution.The present invention carries out mixing pit from bottom of pond portion using solution, while top covers, this knot
Structure can reduce the influence of the evaporation of solution, mixing pool wall solution wall built-up phenomenon to precision preparation.
Detection liquid flow pass 112 of the invention is similarly provided at the bottom of hollow groove, and pipeline is sealed simultaneously in a manner of pressure ring
The stability of solution utilization rate and pipeline can be improved in connection, this structure.In addition this structure can stirrer 73 also at work,
It can be sampled from mixed solution pond 1, when avoiding stirrer 73 and stopping working, mixed solution generates depositional phenomenon, influences water
The analysis of matter analyzer.In addition, to remove the waste sample of front half section when sampling from detection liquid flow pass 112, detection liquid stream is prevented
Channel 112, the dead volume detected in liquid pipe 8 remain out, influence the analysis of Water Test Kits.
The inlet of apocenosis passage 113 is set to the bottom of hollow groove, it can be ensured that the abundant discharge of waste liquid.
The magnetic stirrer 7 includes electromagnet fixing seat 71, electromagnet 72, stirrer 73, the electromagnet fixing seat
71 for electromagnet 72 to be fixed on to the bottom of major trough body 11, and the stirrer 73 is set in hollow groove.
The present invention uses magnetic stirrer 7, and there are two purposes, and one is to speed up the mixing of solution, and two are to speed up major trough body 11
Drying.In solution mixing, since stirrer 73 rotates under the effect of electromagnet 72, by the rotation of stirrer 73, so that
Solution mixes more evenly.When dry, rotated by stirrer 73 and generate wind, hollow groove of the wind of generation in major trough body 11
Rotation accelerates the evaporation of solution on 11 inner wall of major trough body, then by the swabbing action of peristaltic pump 6, by humid air from major trough body
11 extractions, therefore the drying of major trough body 11 is accelerated, avoid raffinate from influencing the configuration precision of solution next time.
The first control signal that the first control module A is used to be issued according to host computer controls the first syringe pump 4 and draws
And push operation, first syringe pump 4 is for drawing standard mother liquid multi-cavity bottle according to first control signal, liquid after absorption
It is pushed in mixed solution pond 1 according to first control signal.
The second control signal that the second control module B is used to be issued according to host computer controls the second syringe pump 5 and draws
And push operation, second syringe pump 5 is for drawing dilution bottle according to second control signal, liquid root after absorption
It is pushed in mixed solution pond 1 according to second control signal.
Third control signal control 6 pairs of mixing of peristaltic pump that the third control module C is used to be issued according to host computer are molten
Liquid pool 1 is aspirated；
The 4th control signal control magnetic stirrer 7 that the circuit control panel is used to be issued according to host computer is stirred
It mixes；
The Water Test Kits is used to detect the liquid come in from detection liquid pipe 8, and will test result and be uploaded to
Host computer；
The host computer is used for the first control module A, the second control module B, third control module C and circuit control
Plate issues first control signal, second control signal, third control signal and the 4th control signal；The host computer is used simultaneously
In the testing result for receiving Water Test Kits, and the water quality point is obtained with the technical indicator of national verification regulation according to testing result
The judgement of analyzer is reported.
A kind of water quality online analyzer calibration method, comprising the following steps:
Step 1, testing staff connects the host computer communication port of the PORT COM of detected Water Test Kits and calibrating installation
It connects, the sampling system of detected Water Test Kits and detection liquid pipe 8 is attached.
Step 2, the standard mother liquid multi-cavity bottle equipped with standard solution mother liquor is connected to the first inlet tube 41；Dilution will be housed
Dilution bottle is connected to the second inlet tube 51；Solution concentration after the concentration and dilution of standard solution mother liquor is input to upper
Machine.
Step 3, host computer calculates according to the solution concentration after the concentration and dilution of standard solution mother liquor and obtains standard solution
The amount of mother liquor and the amount of dilution, and then obtain 5 amount of feed of 4 amount of feed of the first syringe pump and the second syringe pump；Host computer according to
First syringe pump, 4 amount of feed issues first control signal to the first control module A, according to 5 amount of feed of the second syringe pump to second
Control module B issues second control signal, and host computer issues the 4th control signal, to the second control module B to circuit control panel
Issue the 4th control signal.
Step 4, the first control module A controls the first syringe pump 4 according to first control signal and draws mark from standard mother liquid multi-cavity bottle
Quasi- solution mother liquor；Second control module B controls the second syringe pump 5 according to second control signal and draws dilution from dilution bottle；
Second control module B controls the second syringe pump 5 according to second control signal and first injects dilution to mixed solution pond 1, then
First control module A controls the first syringe pump 4 according to first control signal and injects standard solution mother liquor to mixed solution pond 1,
And standard solution mother liquor has at least injected when dilution injection is completed.
Step 5, circuit control panel is stirred driving to stirrer 73 according to the 4th control signal control electromagnet 72, into
And the liquid in mixed solution pond 1 is stirred.
Step 6, after the completion of solution is prepared, computer sends sampling instruction to detected Water Test Kits, is detected water quality
Analyzer carries out sampling operation to solution in mixed solution pond 1 after receiving instruction, is detected Water Test Kits for the analysis of water quality
Information is uploaded to host computer；And the analysis work such as carry out the error of indication, null offset, stability of display, after the completion of analysis will point
Analysis data are sent to computer.
Step 7, host computer analyzes detected Water Test Kits according to the analysis information for being detected Water Test Kits
The automatic calibration of detection, and judgement report is generated, data result can trace to the source.
Automatic calibration refers to the communications protocol that calibrating installation is provided by water quality online analyzer manufacturing enterprise, realization pair
The instruction transmission of instrument and data receiver, by preset program complete to " error of indication " of instrument, " null offset ",
The detection work of projects such as " stability of display ", calibration item can be adjusted according to by the difference of test examination instrument, be not limited to above-mentioned
Three.Automatically it refers to after experimenter selects to carry out experiment option, in entire calibration process, without artificial replacement examination
Agent, without it is artificial it is on duty, be not necessarily to manual record data.Whole process is automatically performed by calibrating installation.
The host computer includes the error of indication, null offset, indicating value to the project of detected Water Test Kits analysis detection
Stability.
The testing process and calculation method (COD) of 7.1 errors of indication
After Water Test Kits stable operation, successively importing mass concentration is CSThe COD standard of (50,150,500mg/L)
Solution measures respectively, and every kind of solution continuously measures 3 times, and the error of indication is calculated as follows:
Wherein, Δ C indicates the error of indication,It indicates to be detected Water Test Kits measurement of concetration average value, CSAfter indicating dilution
Solution concentration.
The testing process and calculation method (COD) of 7.2 null offsets:
After Water Test Kits stable operation, it is molten to mixing that the first syringe pump 4, the second syringe pump 5 are controlled by computer
Liquid pool 1 prepares zero point correction liquid, and prepared zero point correction liquid is imported and is detected Water Test Kits measurement zero point correction liquid, note
Record the initial zero value Z of measurement0, a zero point correction liquid is imported to detected Water Test Kits every 30min in 4h, measures zero
Point indicating value Zi, take and deviate Z0Maximum zero point indicating value ZiAs maximum zero point indicating value Zmax, by maximum zero point indicating value ZmaxWith initial zero
Value Z0Difference as null offset.
7.3 show the testing process and calculation method (COD) for referring to stability:
After Water Test Kits stable operation, it is molten to mixing that the first syringe pump 4, the second syringe pump 5 are controlled by computer
Liquid pool 1 prepares Standard Calibration Solutions；Prepared Standard Calibration Solutions are imported to detected Water Test Kits, record initial measurement
Value S0, continuous operation is for 24 hours；A Standard Calibration Solutions are imported to detected Water Test Kits every 1h interior for 24 hours, measure measurement
Value Si takes and deviates the maximum measured value Si of initial measurement S0 as greatest measurement Smax, calculates indicating value according to following formula
Stability:
Δ S indicates stability of display, SmaxIndicate greatest measurement, S0Indicate initial measurement.
The error of indication, null offset, stability of display's index are to measure the evaluation index of specification Instrumental metering performance, people
When work is evaluated, needs artificial 40 hours on duty and handle data, this calibrating installation is alternative to be manually automatically performed above-mentioned metering performance
Appraisal.
The present invention is to the same Water Test Kits to be detected corresponding various concentration of different detection project in the detection process
The replacement of detection solution realized by the automatic function equipment of solution of calibrating installation, there is no need to manually replace reagent, together
When the present invention using the detection solution of same device proportion various concentration, reduce null offset, stability of display and the error of indication
The human error of testing result.
In addition host computer of the invention can use computer or other central processing units, and each function can be by being based onWindowsAnd WinOperating system is realized, transmittable to do sample instruction and receive data, and will be at data
Reason calculate after formed report and can provide Water Test Kits to be detected whether He Ge conclusion.
Step 8, after the completion of some detectable concentration solution detects, host computer issues third control to third control module C
Signal, third control module C control peristaltic pump and the waste liquid in solution mixing pit are discharged, and waste liquid closes peristaltic pump after excluding, into
The preparation of the next detectable concentration point of row；
It further include to the cleaning of solution mixing pit and dry, side before next detectable concentration point is prepared after waste liquid discharge
Method is as follows: control template B controls the second syringe pump 5 and draws dilution from dilution bottle, is injected into mixed solution pond 1, upper
Machine issues the 4th control signal to circuit control panel, and starting magnetic stirrer 7 cleans mixed solution pond 1, and cleaning finishes,
Signal, which is controlled, by third controls peristaltic pump discharge, so cleaning 3 times or more；It is opened finally, controlling signal control by third
Peristaltic pump, by the 4th control signal enabling magnetic stirrer 7, so that stirrer 73 rotates, and then quickly dry mixed is molten
Liquid pool 1.
The solution uncertainty diluted the present invention is based on calibrating installation less than 3% (k=2), and can by with country
The mode that secondary reference material compares is traced to the source to National primary standard, therefore its Data Data result can trace to the source.
In the present embodiment, the first syringe pump 4 of the invention and the second syringe pump 5 use constant displacement pump, quantitative pump volume:
10ml, when constant displacement pump specification selects between 5ml, 10ml and 25ml, experiments have shown that quantitative injection pump uses the rule of two 10ml
Lattice, operability, the precision highest of solution preparation.Constant displacement pump precision: 2uL/ step.Constant displacement pump motor speed can be according to actual needs
Adjustment, this instrument use speed for 30 revs/min (adjustable), experiments have shown that the pump under the speed pushes volume accuracy highest.
Reset mode: constant displacement pump is mounted with optoelectronic switch in maximum push point (i.e. reset position), first with constant displacement pump before liquid
It resets, to guarantee before preparing solution every time, without being full of dilution in remaining liquid, each pipeline in constant displacement pump.
Remaining liquid control in pipeline: in process for preparation, when carrying out constant displacement pump push, pipeline remains that liquid is full of
State, and by program optimization, remain that the push of mother liquor is first completed, the push of dilution finally completes, and guarantees pipeline
The liquid being inside full of is always dilution (pure water), improves and prepares repdocutbility, to achieve the purpose that control precision.
While taking into account efficiency, the pipeline of latus rectum 2mm is selected, connecting line overall length is short as far as possible, and caliber is as small as possible, subtracts
Few dead volume.Each component is by high temperature resistant, the polytetrafluoro pipe connection of soda acid, and pipe interface is by the way of pressure ring sealing, therefore
Junction contact area is small, and dead volume is small.Compared with raw material band sealing means, leakproofness is more reliable, and operability is more convenient, whole
It is a make sample during, this connection type is completely fixed pipeline, non-loosening phenomenon, reduce detection failure rate.Polytetrafluoro pipe ruler
Very little is 2.85*1.25mm.
Calibrating installation matches liquid, examines through potassium bichromate solution absorbance, and solution prepares error and is less than ± 2%, whole system
There are system deviations, and repeated property test is when host computer generates first control signal and second control signal at this time, middle introducing
System improvement factor K can reduce mechanical liquid mixing system error, so that global error is better than ± 1%.
Water quality online analyzer of the invention is online including being not limited to COD (COD) in-line analyzer, ammonia nitrogen
Analyzer etc. uses water quality parameter point applied to the live non-laboratory of water head site, discharge of industrial wastes mouth, water body environment monitoring point
Analyzer device.
The present invention can one be pushed to field calibration Water Test Kits, the mobility of calibrating installation ensures molten when analysis
Liquid it is ready-to-use, compared with traditional artificial preparation solution is brought to field assay, it is no longer necessary to consider low concentration detect solution
Preservation problem and solution prepare site requirements, solution prepare reproducibility it is higher.
The present invention realizes the Full-automatic calibration to water quality online analyzer, unattended according to predetermined criteria or to want
(such as national metrological verification regulations, the technical specifications such as calibrating standard) are asked, all measuring indexs of water quality online analyzer are carried out
A series of continuous continual analysis tests, acquire data and are analyzed and processed, and determine whether calibration result meets phase
The index request of pass generates corresponding original calibrated report.The reserved output port with external data communication, realizes calibration result
Long-range acquire prepare.Whole process realizes intelligent processing, is not necessarily to manual intervention completely.Meanwhile device has automatic dimension
The function of guarantor, running clearance or standby mode being capable of automatic clean and maintenance, lifting device reliability of operation and stability.
The above is only a preferred embodiment of the present invention, it should be pointed out that: for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (2)
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| CN108982382B (en) * | 2018-07-17 | 2021-05-18 | 厦门市计量检定测试院 | Calibration method of on-line total chromium analyzer |
| CN109752563A (en) * | 2019-03-18 | 2019-05-14 | 青岛埃仑色谱科技有限公司 | Multiple extraction type full-automatic infrared light splitting oil content analyzer, detection method and bearing calibration |
| CN113776618B (en) * | 2021-01-29 | 2023-08-04 | 聚光科技(杭州)股份有限公司 | Self-calibration device and method for liquid volume |
| CN115219680A (en) * | 2022-07-05 | 2022-10-21 | 成都博瑞科传科技有限公司 | A portable water quality monitoring and inspection instrument device and monitoring data correction method |
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| JP4422198B1 (en) * | 2009-02-12 | 2010-02-24 | 株式会社ケット科学研究所 | COD measuring device and measuring method by optical method of rice soup |
| CN102721654B (en) * | 2011-11-16 | 2014-11-05 | 深圳市世纪天源环保技术有限公司 | Background absorption correction method for CODcr measurement |
| CN104483177B (en) * | 2014-12-31 | 2017-09-19 | 力合科技（湖南）股份有限公司 | Water quality automatic sample control method and system |
| CN104535567A (en) * | 2015-01-14 | 2015-04-22 | 成都海兰天澄科技有限公司 | Automatic COD metering method |
| CN107144534A (en) * | 2017-04-21 | 2017-09-08 | 苏州源泓环保科技有限公司 | COD water quality online test method |
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