CN111595306B - Cross section ocean measuring instrument and calibration method thereof - Google Patents
Cross section ocean measuring instrument and calibration method thereof Download PDFInfo
- Publication number
- CN111595306B CN111595306B CN202010596820.7A CN202010596820A CN111595306B CN 111595306 B CN111595306 B CN 111595306B CN 202010596820 A CN202010596820 A CN 202010596820A CN 111595306 B CN111595306 B CN 111595306B
- Authority
- CN
- China
- Prior art keywords
- reagent
- concentration
- instrument
- point
- calibration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01C—MEASURING DISTANCES, LEVELS OR BEARINGS; SURVEYING; NAVIGATION; GYROSCOPIC INSTRUMENTS; PHOTOGRAMMETRY OR VIDEOGRAMMETRY
- G01C13/00—Surveying specially adapted to open water, e.g. sea, lake, river or canal
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01C—MEASURING DISTANCES, LEVELS OR BEARINGS; SURVEYING; NAVIGATION; GYROSCOPIC INSTRUMENTS; PHOTOGRAMMETRY OR VIDEOGRAMMETRY
- G01C25/00—Manufacturing, calibrating, cleaning, or repairing instruments or devices referred to in the other groups of this subclass
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Radar, Positioning & Navigation (AREA)
- Remote Sensing (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Sampling And Sample Adjustment (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention relates to a section ocean measuring instrument, which comprises a shell and an end cover, and is characterized in that: the inside bottom of casing is equipped with the seal pot, be equipped with plunger pump and solenoid valve in the seal pot, plunger pump and solenoid valve all with the valve base bottom surface rigid coupling at seal pot top, valve base top surface is equipped with T shape support, be equipped with modularization liquid way, detection module and main control board on the T shape support, the support top is the end cover, the main control board is connected with modularization liquid way, detection module, plunger pump and solenoid valve electricity, be equipped with inlet, reagent mouth, liquid outlet, mark liquid mouth, electric interface on the end cover. The invention also discloses a calibration method of the profile ocean measuring instrument. The invention mainly uses a spectrophotometry to measure the concentration of seawater substances, and uses the Langmuir beer law to carry out actual measurement, and the calibration method is simple, convenient and efficient.
Description
Technical Field
The invention relates to the technical field of ocean measuring instruments, in particular to a profile ocean measuring instrument and a calibration method thereof.
Background
The ocean measuring instrument based on the spectrophotometry is an important component of the ocean instrument, and the application of the ocean measuring instrument is concentrated on in-situ measurement at the present stage, so that the ocean measuring instrument is widely applied to the market. With the progressive advancement of markets and applications, there are more users desiring to be able to make profile measurements and cruise measurements. In order to meet this requirement, it is necessary to optimize the original instrument.
In order to meet both the sampling rate and the time required for the chemical reaction for field applications, a preferred option for the profilometer is to use flow injection, where no specific reaction components are present, and where after a fixed reaction delay the instrument can be continuously sampled.
Compared with an in-situ measurement instrument, the profile measurement instrument adopting the flow injection method has new requirements on the overall design of the instrument and the requirements of various parts, and further, the calibration process of the profile measurement instrument can meet the requirements by adopting a new method.
Disclosure of Invention
(one) solving the technical problems
The invention mainly solves the technical problems in the prior art, provides a marine measuring instrument convenient for quick and accurate calibration and a calibration method thereof, mainly utilizes a spectrophotometry method to measure the concentration of seawater substances, and applies the Langmuir-Bobber law to carry out actual measurement.
(II) technical scheme
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the utility model provides a section marine survey instrument, includes casing and end cover, the inside bottom of casing is equipped with the seal pot, be equipped with plunger pump and solenoid valve in the seal pot, plunger pump and solenoid valve all with the valve base bottom surface rigid coupling at seal pot top, valve base top surface is equipped with T shape support, be equipped with modularization liquid way, detection module and main control board on the T shape support, the support top is the end cover, the main control board is connected with modularization liquid way, detection module, plunger pump and solenoid valve electricity, be equipped with inlet, reagent mouth, liquid outlet, mark liquid mouth, electrical interface on the end cover.
Further, the liquid path in the modularized liquid path is divided into a sample part, a reagent part and a mixing part, the electromagnetic valve comprises a three-way electromagnetic valve and a two-way electromagnetic valve, the three-way electromagnetic valve and the plunger pump jointly control the circulation of the sample, and the two-way electromagnetic valve controls the circulation of the reagent and the standard liquid.
The invention also provides a calibration method of the profile ocean measuring instrument, which comprises factory calibration and field calibration, wherein the factory calibration comprises the following steps:
1) Determining a minimum concentration of the reagent based on the maximum concentration of the sample;
2) Determining the minimum sample injection rate of the reagent according to the measurement resolution;
3) Calibrating the flow rate of the reagent;
4) Calibrating the LED light source;
5) Calibrating chemical reaction efficiency
6) And calibrating the concentration.
Further, in the step 1), the maximum molar concentration of the sample is a, wherein 1 molecule of the substance to be tested needs to react with n molecules of the reagent, and the minimum molar concentration of the reagent should be n×a.
The minimum sample injection rate of the reagent in the step 2) is as follows
Wherein the movement speed of the instrument is v Dynamic movement The sample injection amount of single sampling is V, the measurement resolution is S, the duty ratio of the sampling time of the plunger pump in the whole working period is tau, and 1 molecule of the detected substance needs to react with n molecules of the reagent.
Further, the step 3) includes the steps of:
3.1 Recording the initial weight of the reagent tank in which the reagent is stored;
3.2 Placing the instrument in water, and keeping the instrument below the water surface;
3.3 The duty ratio is adjusted to be the minimum adjustable duty ratio, the reagent tank is put into water, the instrument is powered off after the time lasts for 30 minutes, the reagent tank is taken out, the external water is wiped off, the weight is recorded after the external water is wiped off, the time and the weight are recorded, and the average flow rate is obtained, wherein the minimum adjustable duty ratio is the percentage of the time delay of a two-way valve switch to the single sample injection time;
3.4 The duty ratio is adjusted to be the maximum adjustable duty ratio, the reagent tank is put into water, the instrument is powered off after the duration is 30 minutes, the reagent tank is taken out, the external water is wiped, the weighing is carried out, the time and the weight are recorded, and the average flow rate is obtained; the sum of the addition of the maximum adjustable duty ratio and the minimum adjustable duty ratio is 1, and is mainly determined by the switch delay of the two-way valve and the single sample injection time;
3.5 The duty ratio is regulated to be 1, the reagent tank is put into water, the instrument is powered off after the duration is 30 minutes, the reagent tank is taken out, the external water is wiped off, the weighing is carried out, the time and the weight are recorded, and the average flow rate is obtained;
3.6 Selecting two duty ratio measuring points between the minimum adjustable duty ratio and the maximum adjustable duty ratio, wherein the two points can generally divide the minimum adjustable duty ratio and the maximum adjustable duty ratio into three parts uniformly, and respectively calculating the average flow velocity of each point;
3.7 And (3) performing curve fitting by using the average flow velocity of each duty ratio measuring point to obtain a function relation of the average flow velocity to the duty ratio, and performing linear fitting.
Further, the step 4) includes the steps of:
4.1 Determining the number of calibration points required by calibration according to application requirements, wherein the minimum number of the calibration points is 5;
4.2 Determining the temperature of each of the calibration points according to the applied temperature range, and distributing the temperature evenly in the temperature range;
4.3 Calibrating the relation between the noise floor of the blank value channel, the influence of water and the temperature, closing the LED, only keeping air in the detection channel, keeping constant temperature for at least one hour at each calibration point, recording the noise floors of the main channel and the reference channel at each calibration point respectively, fitting a curve, and obtaining B Electric power +B Water and its preparation method A curve;
4.4 Calibrating the relation between the blank value channel LED and the temperature, opening the LED, only keeping air in the detection channel, keeping constant temperature for at least one hour at each calibration point, recording signal values of the main channel and the reference channel at each calibration point respectively, fitting a curve, and obtaining C Electric power +C Water and its preparation method Is a curve of (2);
4.5 Using the law of cobobbe, blank value=b Light source ＝B-B Electric power -B Water and its preparation method Color value=c Light source *ρ Chemical treatment ＝C-C Electric power -C Water and its preparation method ；
Where B is the sample value of the blank value channel, B Electric power Noise floor of circuit being blank value channel, B Water and its preparation method Is the background influence of the water body of the blank value channel, C is the sampling value of the main light path of the color development value channel, C Electric power Noise floor of circuit of main light path of color value channel, C Water and its preparation method Is the background influence of the water body of the main light path of the color development value channel, C Light source Is the response of the luminous intensity of the light source LED at the receiving end, ρ Chemical treatment After the substance to be detected in the sample reacts with the chemical reagentThe effect of the generation.
Further, the step 5) includes the steps of:
5.1 Determining a fixed point number, 5 points or 7 points according to the application condition;
5.2 Determining the temperature of the standard points, and evenly distributing the standard points in a temperature range, wherein the distance between the temperature points is not less than 5 ℃;
5.3 Selecting a certain concentration standard solution, wherein the test value of the standard solution at the highest temperature point and the lowest temperature point is not more than the linear interval of the measuring range of the instrument;
5.4 Sequentially heating the standard liquid to the temperatures of all the standard points, keeping the temperature for one hour, and measuring and recording the numerical values;
5.5 Fitting the obtained data to obtain a curve formula.
Further, the step 6) includes the steps of:
6.1 Selecting a constant temperature point, and selecting a temperature of 25 ℃ or 300 Kelvin at normal temperature;
6.2 Selecting concentration calibration points in a target range, selecting at least 5 points, and meeting a 2-time relation between the concentrations of other adjacent points except for a concentration zero point;
6.3 Placing the instrument, the reagent tank, the standard solution and the like into a constant temperature box, and keeping the temperature at a constant temperature point for 1 hour;
6.4 Taking the standard solution with the concentration of 0 as a sample, starting measurement, continuously recording all blank value and color development value data for 1 hour, powering off the instrument, and replacing the reagent;
6.5 Repeating the previous step according to the sequence from small to large in concentration under the condition of using standard liquids with different concentrations, and recording all data in the middle;
6.6 Drawing blank value and color development value curves according to the time point sequence;
6.7 Removing abnormal points in the curve which can be reasonably interpreted;
6.8 Averaging the blank value and the color value in each data interval in different concentration ranges, wherein the average values represent the blank value and the color value at each concentration point;
6.9 Applying the Langmuir law to the average value of the blank value and the color value to obtain the absorbance of each point;
6.10 Fitting the relation between the absorbance and the concentration of each point according to the linear relation.
Further, the field calibration comprises the following steps:
1) Closing the sample inlet, opening the standard liquid port, and taking the liquid in the standard liquid bag in the reagent tank as a test sample;
2) The sample injection speed of the standard solution is regulated to make the concentration of the standard solution be half of the full range of the instrument, and the water sample residue on the site is flushed for 10 minutes or until the sampling data is re-stabilized;
3) Starting a detection module, starting measurement, lasting for 30 minutes, and recording all data;
4) Removing abnormal points which can be reasonably interpreted;
5) In the data smoothing stage, the blank value and the color development value are averaged to represent the blank value and the color development value of the concentration point;
6) Applying the Lanboll law to obtain the absorbance of the point;
7) And performing curve translation according to the relation between the half-range concentration point on the factory calibration curve and the on-site half-range concentration point data.
Advantageous effects
The invention provides a method for preparing the composite material, which has the following beneficial effects:
1. the ocean measuring instrument adopts the plunger pump and the electromagnetic valve as power, is convenient to measure by using a flow injection method, has adjustable space and is convenient to calibrate, thereby realizing more accurate profile measurement;
2. the T-shaped bracket is adopted, so that the positions of all the parts are relatively independent, and mutual interference is avoided;
3. when the plant is calibrated, the influence of main factors of measurement on a measurement result is avoided through calibrating the flow rate, the LED light source, the chemical reaction efficiency and the concentration, the measurement accuracy of an instrument is improved, and the calibration method is accurate and efficient;
4. when in field calibration, the data correction can be carried out to a certain extent by a simple calibration method, and the measurement accuracy of the instrument is improved.
Drawings
FIG. 1 is a schematic diagram of the structure of the present invention;
FIG. 2 is a schematic view of the structure of the end cap of the present invention;
FIG. 3 is a schematic view of the structure of the present invention in a housing;
FIG. 4 is a schematic view of the structure of the bracket of the present invention;
FIG. 5 is a schematic diagram of a single parameter fluid circuit according to the present invention;
wherein 1 is an end cover, 2 is a shell, 3 is an electrical interface, 4 is a liquid inlet, 5 is a reagent port, 6 is a standard liquid port, 7 is a liquid outlet, 8 is a modularized liquid path, 9 is a detection module, 10 is a plunger pump, 11 is an internal support, 12 is a main control board, 13 is a valve base, 14 is an electromagnetic valve, and 15 is a sealing tank.
The specific embodiment is as follows:
the technical scheme of the invention is further specifically described below through examples and with reference to the accompanying drawings.
Example 1
As shown in fig. 1 to 4, the cross-section ocean measuring instrument comprises an end cover 1, a shell 2, a main control board 12, a detection module 9, an internal bracket 11, a modularized liquid path 8, a plunger pump 10, an electromagnetic valve 14, a valve base 13, a sealing tank 15, a water pipe and a connector for liquid path connection, an electric wire and a connector for electric connection and the like (not shown in the figure).
The end cover 1 is combined with the shell 2 to protect other components of the instrument and provide certain compression resistance and watertight capability for the components. In addition, the end cover is also an external interface of the whole instrument, and is provided with an electric interface 3, a liquid inlet 4, a reagent port 5, a standard liquid port 6, a liquid outlet 7, and functions of electric connection, a communication interface, sample sampling, reagent addition, waste liquid discharge and the like are performed with the outside, and if necessary, a pretreatment device is further added at a sample sampling position according to the need, so as to perform pretreatment of a sample, and the pretreatment device is used for removing various substances which influence measurement and are contained in the sample.
The main control board 12 is a core for controlling the whole instrument circuit and is used for controlling various parts of the bottom layer of the instrument. And receiving an instruction from the upper computer, performing parameter setting of instrument operation, sampling in real time, storing data to a designated position, and transmitting the data according to requirements.
The detection module 9 is a technical key point of the whole instrument and is used for detecting blank values and color development values of the substance to be detected, and based on the blank values and the color development values, the concentration of the substance to be detected can be calculated by applying the Bobber law. When the detection module is applied to the single parameter module, the detection module comprises a blank value channel and a color development value channel, the two channels are identical, and the specific function of each channel is determined by a waterway connection mode.
The internal support 11 is used for placing all the components except the sealing tank inside the instrument, and placing all the components on different sides of the internal support can effectively isolate water and electricity, and is easy to install and maintain.
The modularized liquid path 8 internally comprises a more complex liquid path, and compared with a liquid path simply composed of water pipes, the modularized liquid path has the advantages of less occupied space, higher pressure resistance and being particularly suitable for the condition of more complex liquid path conditions, such as multiple parameters. In addition, the device is flexible in design, and can meet the requirements of various different measuring methods of the same parameter without affecting other components of the instrument.
The plunger pump 10 is a sample injection device of the instrument, is a main power unit of the instrument, and can effectively control the sample injection amount of a sample during single sample injection by using different clock signals and setting different strokes. When the device is used together with the three-way electromagnetic valve, the flow direction of a sample can be effectively controlled.
The solenoid valve 4 functions to control the flow of liquid and the closed state, and in the present invention, a three-way solenoid valve and a two-way solenoid valve are used. Wherein, the three-way electromagnetic valve and the plunger pump jointly act to control sample injection of the sample. The two-way electromagnetic valve is independently used for controlling the circulation of the reagent, and the sample injection quantity and sample injection time of the reagent can be effectively controlled through the duty ratio of the working time of the two-way electromagnetic valve.
The valve base 13 is an important base point for the normal operation of the solenoid valve and plunger pump, which need to be fixed on a relatively stable solenoid valve base, and the specificity of the inlet ports of the solenoid valve and plunger pump also determines the need for a separate solenoid valve base design.
The sealing tank 15 plays a certain sealing role, protects the plunger pump and the electromagnetic valve in the sealing tank, combines the sealing tank with the valve base, provides certain compression-resistant protection and watertight protection for the plunger pump and the electromagnetic valve, and can enable the plunger pump and the electromagnetic valve to work normally under certain pressure.
The inside of instrument adopts T type supporting structure, looks down from the instrument end cover promptly, becomes T type between the inside, in every frame, distributes threaded hole and the bar hole that has not the same size, and the benefit of doing so includes following points:
multiple sections can be formed, so that the overall layout of accessories for different purposes is facilitated;
the circuit component and the waterway component are effectively separated, so that mutual interference is avoided;
the installation and maintenance are easy, and the target component can be directly operated without affecting other parts;
each component in the frame can be finely tuned to a certain extent;
is beneficial to the arrangement of the water pipe and the electric wire.
The liquid path can be divided into 3 parts according to different liquid components, namely: a sample portion, a reagent portion, a mixing portion. Wherein only the sample portion is in fluid communication with the reagent portion and only the reagent portion is in fluid communication with the mixing portion. The three sections are interconnected on a modular fluid path.
The fluid path of a typical single parameter profile marine instrument should be as shown in fig. 5.
The sample enters the instrument from the liquid inlet of the instrument end cover, flows through the blank value channel of the detection module after entering the instrument, and finally flows into the sample input port of the modularized liquid path.
The reagent enters the instrument from the reagent port of the instrument end cover, flows through the two-way valve after entering the instrument, and finally flows into the reagent input port of the modularized liquid path.
After the sample and the reagent flow into the modularized liquid path, the mixing is started to perform chemical reaction, mixed liquid flows out of the modularized liquid path and flows into a color development value channel of the detection module, then the mixed liquid is sent into the plunger pump, and finally the mixed liquid is discharged out of the instrument through a liquid outlet of an instrument end cover by the plunger pump.
Example 2
The instrument is subjected to factory calibration before factory shipment, and is subjected to field calibration when in use.
The factory calibration includes the following steps.
1) Application analysis
When the instrument is applied on site, a plurality of influencing factors exist, and in the factory calibration stage, the following two points need to be considered in an important way, namely: maximum concentration of analyte and measurement resolution.
The maximum concentration of the to-be-detected object determines the minimum concentration of the reagent, generally, the requirement that the reagent is enough and cannot be less than the measuring range of the instrument is met, and the sample injection ratio of the sample to the reagent is further determined.
Assuming that the maximum molar concentration of the target sample is a, 1 molecule of the substance to be tested needs to react with n molecules of the reagent to generate the desired chromogenic substance according to the chemical reaction requirement, then the minimum molar concentration of the reagent should be n×a.
The measurement resolution refers to the distance of instrument movement in one measurement period, the higher the resolution, the denser the sampling points are, the faster the sample injection rate of a single point is required, and the minimum sample injection rate of the reagent can be obtained by considering the sample injection ratio of the sample and the reagent.
Assuming that in certain applications the instrument moves at a velocity v Dynamic movement The working period is T, the measurement resolution is S, and the measurement resolution is
S＝v Dynamic movement *T
Assuming that the sampling time of the plunger pump occupies the duty ratio of the whole working period to be tau, the sampling amount of single sampling is V, and the sampling rate is V Mixing Then
V＝v Mixing *T*τ
Combining the two types to obtain
It can be seen that, under the condition of a certain movement rate of the instrument, the higher the measurement resolution is, the smaller the measurement distance is, and the higher the sample injection rate of the instrument is required.
Further, the minimum sample injection rate of the instrument reagent
v Dynamic movement ＝v Mixing *n
2) Flow rate calibration
In the invention, the driving force of the sample and the reagent is from the plunger pump, and the sample and the reagent are used for dividing the flow rate provided by the plunger pump and sharing the flow rate of the plunger pump together. The on-off of the two-way valve can be controlled through the circuit function, and the sample injection quantity of the reagent can be adjusted by utilizing the conduction time of the two-way valve.
The reagent flow rate calibration can be performed according to the following steps:
record the initial weight of the reagent tank holding the reagent;
placing the instrument in water, kept below the water surface;
the duty ratio is adjusted to be the minimum adjustable duty ratio, the reagent tank is put into water, the instrument is powered off after the duration is 30 minutes, the reagent tank is taken out, the external water is wiped off, the weighing is carried out, the time and the weight are recorded, and the average flow rate is obtained; the minimum adjustable duty ratio is the percentage of the time delay of the two-way valve switch to the single sample injection time;
the duty ratio is adjusted to be the maximum adjustable duty ratio, the reagent tank is put into water, the instrument is powered off after the duration is 30 minutes, the reagent tank is taken out, the external water is wiped off, the weighing is carried out, the time and the weight are recorded, and the average flow rate is obtained; the sum of the addition of the maximum adjustable duty ratio and the minimum adjustable duty ratio is 1, and is mainly determined by the switch delay of the two-way valve and the single sample injection time;
the duty ratio is regulated to be 1, the reagent tank is put into water, the instrument is powered off after the duration is 30 minutes, the reagent tank is taken out, the external water is wiped off, the weighing is carried out, the time and the weight are recorded, and the average flow rate is obtained;
selecting two duty ratio measuring points between the minimum adjustable duty ratio and the maximum adjustable duty ratio, wherein the two points can generally divide the minimum adjustable duty ratio and the maximum adjustable duty ratio into three parts uniformly, and respectively calculating the average flow velocity of each point;
curve fitting is performed by using the average flow velocity of each duty cycle measurement point, so that a functional relation between the average flow velocity and the duty cycle can be obtained, and linear fitting is generally used;
in most cases, the sample injection speed required by the reagent and the sample is very different, and the sample injection speed required by the reagent is far smaller than that of the sample, and in practical application, the sample injection speed of the sample can be approximately calculated according to the sample injection speed of the plunger pump, namely, the sample injection speed is a fixed value. On the basis, the adjustment of the duty ratio of the reagent can be performed according to a larger step length, so that the corresponding sample and reagent sample injection speed ratio can be achieved.
3) Calibration of LED light source
In the invention, the light source receiving end receives and samples the photoelectric signal, and the photoelectric signal is expressed in the form of digital quantity, and the variables are all digital quantity, no unit exists, and the relation between the required unit and the digital quantity can be automatically derived according to the situation if the unit exists.
The following relationship is satisfied at the blank value channel:
B＝B electric power ＋B Water and its preparation method ＋B Light source
Wherein B is a sampling value of a blank value channel; b (B) Electric power Noise floor of the circuit that is a blank value channel; b (B) Water and its preparation method Is the background influence of the water body of a blank value channel, mainly reflects the influence of factors such as turbidity, fluorescence and the like of the water body, and has a value far smaller than B in the application of a spectrophotometry Light source The method is generally negligible, and can be used as a constant value for calculation and be incorporated into circuit noise when the influence is large and cannot be ignored; b (B) Light source Is the response of the luminous intensity of the light source LED at the receiving end.
Similarly, the following relationship is satisfied at the color value channel:
C＝C electric power +C Water and its preparation method +C Light source *ρ Chemical treatment
Wherein C is a sampling value of a main light path of the color development value channel; c (C) Electric power Is the main light path of the color development value channelIs a noise floor of the circuit; c (C) Water and its preparation method Is the background influence of the water body of the main light path of the color development value channel; c (C) Light source Is the response of the luminous intensity of the light source LED at the receiving end; ρ Chemical treatment The influence of the substances to be detected in the sample after the reaction with the chemical reagent can reduce the intensity of the light beam, and the higher the concentration is, the more remarkable the reduction is.
In the invention, the relation between the luminous intensity and the temperature of the LED is required to be calibrated before the instrument is used, and a basis is provided for the later data correction.
The specific operation is as follows:
determining the number of calibration points required for calibration according to application requirements, and generally suggesting 7 points or 9 points, and at least 5 points in a laboratory;
determining the temperature of each of the calibration points according to the temperature range of the application, generally suggesting an average distribution over the temperature range;
calibration of the relation between blank value channel noise floor, water influence and temperature: closing the LED, only keeping air in the detection channel, keeping constant temperature for at least one hour at each calibration point, recording noise floors of the main channel and the reference channel at each calibration point respectively, and fitting a curve to obtain B Electric power +B Water and its preparation method A curve;
calibration of the relation of the blank value channel LED to temperature: turning on the LED, only keeping air in the detection channel, keeping constant temperature at each calibration point for at least one hour, recording signal values of the main channel and the reference channel at each calibration point, fitting a curve to obtain C Electric power +C Water and its preparation method Is a curve of (2);
when the law of Bobber is applied, blank value=B Light source ＝B-B Electric power -B Water and its preparation method Color value=c Light source *ρ Chemical treatment ＝C-C Electric power -C Water and its preparation method ；
4) Calibration of chemical reaction efficiency
In the invention, the influence of temperature on chemical reaction can be corrected by a calibration method, and the specific flow is as follows:
determining a fixed point number, 5 points or 7 points according to the application condition;
determining the temperature of the standard points, generally evenly distributing in a temperature range, and suggesting that the temperature point spacing is not less than 5 ℃;
selecting a concentration of the standard solution, wherein the test value of the concentration of the standard solution at the highest temperature point and the lowest temperature point is not more than the linear interval of the measurement range of the instrument;
heating the standard liquid to the temperatures of all the standard points in sequence, keeping the temperature for one hour, and measuring and recording the numerical values;
fitting the obtained data to obtain a curve formula;
in the present invention, a temperature sensor is added to measure the water temperature, and the temperature sensor is generally placed in the liquid path before the inlet of the detection module.
5) Concentration calibration
In the invention, the main application of the franbiot law, according to the previous procedure, has calibrated the effect of temperature on the measurement result, and the concentration calibration is carried out at a constant temperature.
The concentration calibration step comprises the following steps:
selecting a constant temperature point, suggesting a normal temperature, i.e. 25 degrees celsius or 300 kelvin;
selecting a concentration calibration point number in a target range, suggesting 5 points, wherein the concentrations of other adjacent points except the concentration zero point satisfy a 2-time relation;
placing the instrument, reagent tank, label solution, etc. into an incubator, and keeping the temperature at the constant temperature point for 1 hour;
taking a standard solution with the concentration of 0 as a sample, starting measurement, continuously recording all blank value and color development value data for 1 hour, powering off the instrument, and replacing the reagent;
repeating the previous step in the order of the concentration from small to large under the condition of using the standard liquid with different concentrations, and recording all data in the middle;
drawing blank value and color development value curves according to the time point sequence;
removing abnormal points which can be reasonably interpreted from the curve, such as obvious points containing bubbles, pseudo data points caused by switching on and switching off, data fluctuation in the LED preheating stage and the like;
averaging the blank value and the color value of each data interval in different concentration ranges, wherein the average value represents the blank value and the color value at each concentration point;
applying the mean of these blank and color values, applying the Bobber's law, obtaining the absorbance of each point;
fitting the relation between the absorbance and the concentration of each point according to the linear relation;
in field applications, the parameters of the instrument drift along with the combined action of the service time and various stresses, and sometimes seriously affect the accuracy of the instrument, so that calibration is needed again for correction, and calibration is needed in the field.
The field calibration can be performed as follows.
Closing the sample inlet, opening the standard liquid port, and taking the liquid in the standard liquid bag in the reagent tank as a test sample;
regulating the sample injection speed of the standard solution by software to ensure that the concentration of the standard solution is half of the full range of the instrument, flushing the water sample residue on site, and lasting for 10 minutes or until the sampling data are re-stabilized;
starting the detection module, starting measurement, lasting 30 minutes, and recording all data;
removing abnormal points which can be reasonably interpreted, such as obvious points containing bubbles, pseudo data points caused by switching on and switching off, data fluctuation in the LED preheating stage and the like;
averaging the blank value and the color development value in the data smoothing stage, wherein the blank value and the color development value represent the concentration point;
applying the Bobber's law to obtain the absorbance at that point;
performing curve translation according to the relation between the half-range concentration point on the original factory calibration curve and the on-site half-range concentration point data
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (5)
1. The utility model provides a calibration method of section marine survey instrument, this section marine survey instrument includes casing and end cover, its characterized in that: the bottom end inside the shell is provided with a sealing tank, the sealing tank is internally provided with a plunger pump and an electromagnetic valve, the plunger pump and the electromagnetic valve are fixedly connected with the bottom surface of a valve base at the top of the sealing tank, the top surface of the valve base is provided with a T-shaped bracket, the T-shaped bracket is provided with a modularized liquid path, a detection module and a main control board, the top of the T-shaped bracket is an end cover, the main control board is electrically connected with the modularized liquid path, the detection module, the plunger pump and the electromagnetic valve, be equipped with inlet, reagent mouth, liquid outlet, mark liquid mouth, electrical interface on the end cover, liquid way in the modularization liquid way divide into sample part, reagent part, mixed part, the solenoid valve includes three solenoid valve and two solenoid valves, three solenoid valve and plunger pump jointly control the circulation of sample, two solenoid valves control the circulation of reagent and mark liquid, its characterized in that: the method comprises factory calibration and field calibration;
the factory calibration includes the following steps,
1) Determining the lowest concentration of a reagent according to the maximum concentration of a sample, wherein the maximum molar concentration of the sample is a, 1 tested substance molecule needs to react with n reagent molecules, and the lowest molar concentration of the reagent is n;
2) Determining the minimum sample injection rate of the reagent according to the measurement resolution, wherein the minimum sample injection rate of the reagent is as follows
Wherein the movement speed of the instrument is v Dynamic movement The sample injection amount of single sampling is V, the measurement resolution is S, the duty ratio of the sampling time of the plunger pump in the whole working period is tau, and 1 detected substance molecule needs to react with n reagent molecules;
3) Calibrating the flow rate of the reagent;
4) Calibrating the LED light source;
5) Calibrating the chemical reaction efficiency;
6) Calibrating the concentration;
the field calibration comprises the steps of,
1) Closing the sample inlet, opening the standard liquid port, and taking the liquid in the standard liquid bag in the reagent tank as a test sample;
2) The sample injection speed of the standard solution is regulated to make the concentration of the standard solution be half of the full range of the instrument, and the water sample residue on the site is flushed for 10 minutes or until the sampling data is re-stabilized;
3) Starting a detection module, starting measurement, lasting for 30 minutes, and recording all data;
4) Removing abnormal points which can be reasonably interpreted;
5) In the data smoothing stage, the blank value and the color development value are averaged to represent the blank value and the color development value of the concentration point;
6) Applying the Lanboll law to obtain the absorbance of the point;
7) And performing curve translation according to the relation between the half-range concentration point on the factory calibration curve and the on-site half-range concentration point data.
2. The calibration method of a profile marine surveying instrument according to claim 1, wherein: the step 3) of factory calibration comprises the following steps:
3.1 Recording the initial weight of the reagent tank in which the reagent is stored;
3.2 Placing the instrument in water, and keeping the instrument below the water surface;
3.3 The duty ratio is adjusted to be the minimum adjustable duty ratio, the reagent tank is put into water, the instrument is powered off after the time lasts for 30 minutes, the reagent tank is taken out, the external water is wiped off, the weight is recorded after the external water is wiped off, the time and the weight are recorded, and the average flow rate is obtained, wherein the minimum adjustable duty ratio is the percentage of the time of single sample injection occupied by the time delay of the two-way electromagnetic valve switch;
3.4 The duty ratio is adjusted to be the maximum adjustable duty ratio, the reagent tank is put into water, the instrument is powered off after the duration is 30 minutes, the reagent tank is taken out, the external water is wiped, the weighing is carried out, the time and the weight are recorded, and the average flow rate is obtained; the sum of the addition of the maximum adjustable duty ratio and the minimum adjustable duty ratio is 1, and is determined by the switch delay of the two-way electromagnetic valve and the single sample injection time;
3.5 The duty ratio is regulated to be 1, the reagent tank is put into water, the instrument is powered off after the duration is 30 minutes, the reagent tank is taken out, the external water is wiped off, the weighing is carried out, the time and the weight are recorded, and the average flow rate is obtained;
3.6 Selecting two duty ratio measuring points between the minimum adjustable duty ratio and the maximum adjustable duty ratio, wherein the two measuring points can uniformly divide the minimum adjustable duty ratio and the maximum adjustable duty ratio into three parts, and respectively calculating the average flow velocity of each point;
3.7 And (3) performing curve fitting by using the average flow velocity of each duty ratio measuring point to obtain a function relation of the average flow velocity to the duty ratio, and performing linear fitting.
3. A method of calibrating a profile marine surveying instrument according to claim 2, wherein: the step 4) of factory calibration comprises the following steps:
4.1 Determining the number of calibration points required by calibration according to application requirements, wherein the minimum number of the calibration points is 5;
4.2 Determining the temperature of each of the calibration points according to the applied temperature range, and distributing the temperature evenly in the temperature range;
4.3 Calibrating the relation between the noise floor of the blank value channel, the influence of water and the temperature, closing the LED, only keeping air in the detection channel, keeping constant temperature for at least one hour at each calibration point, recording the noise floors of the main channel and the reference channel at each calibration point respectively, fitting a curve, and obtaining B Electric power +B Water and its preparation method A curve;
4.4 Calibrating the relation between the blank value channel LED and the temperature, opening the LED, only keeping air in the detection channel, keeping constant temperature for at least one hour at each calibration point, recording signal values of the main channel and the reference channel at each calibration point respectively, fitting a curve, and obtaining C Electric power +C Water and its preparation method Is a curve of (2);
4.5 Using the law of cobobbe, blank value = B-B Electric power -B Water and its preparation method ，
Color value = C Light source *ρ Chemical treatment ＝C-C Electric power -C Water and its preparation method ；
Where B is the sample value of the blank value channel, B Electric power Noise floor of circuit being blank value channel, B Water and its preparation method Is the background influence of the water body of the blank value channel, C is the sampling value of the main light path of the color development value channel, C Electric power Noise floor of circuit of main light path of color value channel, C Water and its preparation method Is the background influence of the water body of the main light path of the color development value channel, C Light source Is the response of the luminous intensity of the light source LED at the receiving end, ρ Chemical treatment Is the effect of the reaction of the substance to be measured in the sample with the chemical reagent.
4. A method of calibrating a profile marine surveying instrument according to claim 3, wherein: the step 5) of factory calibration comprises the following steps:
5.1 Determining a fixed point number, 5 points or 7 points according to the application condition;
5.2 Determining the temperature of the standard points, and evenly distributing the standard points in a temperature range, wherein the distance between the temperature points is not less than 5 ℃;
5.3 Selecting a corresponding concentration standard solution, wherein the test value of the corresponding concentration standard solution at the highest temperature point and the lowest temperature point is not more than the linear interval of the measuring range of the instrument;
5.4 Sequentially heating the standard liquid to the temperatures of all the standard points, keeping the temperature for one hour, and measuring and recording the numerical values;
5.5 Fitting the obtained data to obtain a curve formula.
5. The method for calibrating a profile marine surveying instrument according to claim 4, wherein: the step 6) of factory calibration comprises the following steps:
6.1 Selecting a constant temperature point, and selecting a temperature of 25 ℃ or 300 Kelvin at normal temperature;
6.2 Selecting concentration calibration points in a target range, selecting at least 5 points, and meeting a 2-time relation between the concentrations of other adjacent points except for a concentration zero point;
6.3 Placing the instrument, the reagent tank and the standard solution into a constant temperature box, and keeping the temperature at a constant temperature point for 1 hour;
6.4 Taking the standard solution with the concentration of 0 as a sample, starting measurement, continuously recording all blank value and color development value data for 1 hour, powering off the instrument, and replacing the reagent;
6.5 Repeating the previous step according to the sequence from small to large in concentration under the condition of using standard liquids with different concentrations, and recording all data in the middle;
6.6 Drawing blank value and color development value curves according to the time point sequence;
6.7 Removing abnormal points in the curve which can be reasonably interpreted;
6.8 Averaging the blank value and the color value in each data interval in different concentration ranges, wherein the average values represent the blank value and the color value at each concentration point;
6.9 Applying the Langmuir law to the average value of the blank value and the color value to obtain the absorbance of each point;
6.10 Fitting the relation between the absorbance and the concentration of each point according to the linear relation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010596820.7A CN111595306B (en) | 2020-06-28 | 2020-06-28 | Cross section ocean measuring instrument and calibration method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010596820.7A CN111595306B (en) | 2020-06-28 | 2020-06-28 | Cross section ocean measuring instrument and calibration method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111595306A CN111595306A (en) | 2020-08-28 |
| CN111595306B true CN111595306B (en) | 2023-05-16 |
Family
ID=72182540
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010596820.7A Active CN111595306B (en) | 2020-06-28 | 2020-06-28 | Cross section ocean measuring instrument and calibration method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111595306B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116608887B (en) * | 2023-07-17 | 2023-10-13 | 山东科技大学 | Disposable ocean current profiler test calibration device and method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105929124A (en) * | 2016-06-12 | 2016-09-07 | 深圳市清时捷科技有限公司 | On-line water quality analysis instrument and water quality analysis method thereof |
| CN110927235A (en) * | 2019-12-11 | 2020-03-27 | 中兴仪器（深圳）有限公司 | On-line analyzer and measuring method for trace iodine |
| CN111289504A (en) * | 2020-03-13 | 2020-06-16 | 国家深海基地管理中心 | Deep sea in-situ detection instrument and method for dissolved iron and ferrous iron |
| CN111337483A (en) * | 2020-02-18 | 2020-06-26 | 青岛卓建海洋装备科技有限公司 | Seawater ammonia nitrogen concentration online detection device and method |
-
2020
- 2020-06-28 CN CN202010596820.7A patent/CN111595306B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105929124A (en) * | 2016-06-12 | 2016-09-07 | 深圳市清时捷科技有限公司 | On-line water quality analysis instrument and water quality analysis method thereof |
| CN110927235A (en) * | 2019-12-11 | 2020-03-27 | 中兴仪器（深圳）有限公司 | On-line analyzer and measuring method for trace iodine |
| CN111337483A (en) * | 2020-02-18 | 2020-06-26 | 青岛卓建海洋装备科技有限公司 | Seawater ammonia nitrogen concentration online detection device and method |
| CN111289504A (en) * | 2020-03-13 | 2020-06-16 | 国家深海基地管理中心 | Deep sea in-situ detection instrument and method for dissolved iron and ferrous iron |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111595306A (en) | 2020-08-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN201331497Y (en) | Permanganate index on-line automatic monitor device | |
| CN103033499B (en) | A kind of water quality analytical system | |
| CN108663347A (en) | Optical dissolved oxygen sensor multi-parameter interference compensation corrects system and method | |
| CN108680551B (en) | In-situ self-calibration device and method for optical dissolved oxygen sensor | |
| AU2007324277B2 (en) | Chemical analyser | |
| JP4819816B2 (en) | Biogas measuring apparatus and method for measuring volume of biogas | |
| CN208537414U (en) | Optical dissolved oxygen sensor multi-parameter interference compensation corrects system | |
| US8077311B1 (en) | Spectrophotometric system for simultaneous flow-through measurements of dissolved inorganic carbon, pH and CO2 fugacity | |
| CN111595306B (en) | Cross section ocean measuring instrument and calibration method thereof | |
| Pinto et al. | A low-cost lab-on-a-chip device for marine pH quantification by colorimetry | |
| CN106198532A (en) | The dual wavelength autocontrol method of a kind of quick photometric titration and device | |
| CN111289503B (en) | Instrument and method for in-situ detection of deep-sea dissolved sulfide | |
| JP2022510518A (en) | Spectral potential temperature multidimensional titration analyzer and its usage | |
| Johnson et al. | Continuous determination of nitrate concentrations in situ | |
| CN100567953C (en) | A kind of sea water COD automatic detector | |
| CN111458319B (en) | Device and method for online determination of ammonia nitrogen concentration in water body | |
| Shangguan et al. | Automated spectrophotometric determination of carbonate ion concentration in seawater using a portable syringe pump based analyzer | |
| CN109709197B (en) | BOD rapid tester and accurate compensation testing method | |
| CN209673712U (en) | BOD Quick testing instrument | |
| CN208795660U (en) | Optical dissolved oxygen sensor original position self-calibrating device | |
| CN108796005A (en) | A kind of method of real-time monitoring Corynebacterium glutamicum fermentation process | |
| CN212301399U (en) | Ocean carbon dioxide on-line monitoring system based on electrochemical sensing | |
| JP2001318057A (en) | Residual chlorine measuring method and its device | |
| CN201740741U (en) | Portable multifunctional color comparator | |
| CN112378867A (en) | Water quality analyzer and liquid path cleaning method of water quality analyzer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |