CN111595306A - Profile marine measuring instrument and calibration method thereof - Google Patents
Profile marine measuring instrument and calibration method thereof Download PDFInfo
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- CN111595306A CN111595306A CN202010596820.7A CN202010596820A CN111595306A CN 111595306 A CN111595306 A CN 111595306A CN 202010596820 A CN202010596820 A CN 202010596820A CN 111595306 A CN111595306 A CN 111595306A
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- 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
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- G—PHYSICS
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- G01C—MEASURING DISTANCES, LEVELS OR BEARINGS; SURVEYING; NAVIGATION; GYROSCOPIC INSTRUMENTS; PHOTOGRAMMETRY OR VIDEOGRAMMETRY
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Abstract
The invention relates to a section marine measuring instrument, which comprises a shell and an end cover, and is characterized in that: the bottom of the interior of the shell is provided with a seal pot, a plunger pump and an electromagnetic valve are arranged in the seal pot, the plunger pump and the electromagnetic valve are fixedly connected with the bottom surface of a valve base at the top of the seal pot, a T-shaped support is arranged on the top surface of the valve base, a modular liquid path, a detection module and a main control board are arranged on the T-shaped support, the top of the support is an end cover, the main control board is electrically connected with the modular liquid path, the detection module, the plunger pump and the electromagnetic valve, and an inlet, a reagent port, a liquid outlet, a standard liquid port and an electrical interface are arranged on the. The invention also discloses a calibration method of the profile marine measuring instrument. The invention mainly utilizes a spectrophotometer method to measure the concentration of seawater substances, and applies the Law of Lanberger 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 marine measuring instruments, in particular to a profile marine measuring instrument and a calibration method thereof.
Background
The marine measuring instrument based on the spectrophotometer method is an important component of the marine instrument, and at the present stage, the application of the instrument is concentrated on in-situ measurement and is widely applied in the market. With the progressive market and application, more users want to be able to make profile measurements and cruise measurements. In order to meet the requirement, optimization needs to be carried out on the basis of the original instrument.
In order to take into account the requirements of field applications for sampling rate and time required for chemical reactions, a better choice for a profiling instrument is to use flow injection, which has no specific reaction components, and the instrument can sample continuously after a fixed reaction delay.
Compared with an in-situ measuring instrument, the profile measuring instrument using 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 measuring instrument can meet the requirements only by applying a new method.
Disclosure of Invention
Technical problem to be solved
The invention mainly solves the technical problems in the prior art, provides the marine measuring instrument convenient for quick and accurate calibration and the calibration method thereof, mainly utilizes a spectrophotometer method to measure the concentration of seawater substances, and applies the Law of Lanberger to carry out actual measurement.
(II) technical scheme
In order to achieve the purpose, the invention adopts the following technical scheme:
the utility model provides a section marine measuring 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.
Furthermore, 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 section marine measuring instrument, which comprises factory calibration and field calibration, wherein the factory calibration comprises the following steps:
1) determining the minimum concentration of the reagent according to the maximum concentration of the sample;
2) determining the minimum sample introduction 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, the maximum molarity of the sample in step 1) is a, wherein 1 molecule of the substance to be detected needs to react with n molecules of the reagent, and the minimum molarity of the reagent should be n x a.
The minimum sample introduction rate of the reagent in the step 2) is
Wherein the instrument has a speed of movement vMovable partThe sampling volume 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 measured substance molecule needs to react with n reagent molecules.
Further, the step 3) comprises the following steps:
3.1) recording the initial weight of the reagent tank storing the reagent;
3.2) putting the instrument into water and keeping the instrument below the water surface;
3.3) adjusting the duty ratio to be the minimum adjustable duty ratio, putting the reagent tank into water, powering off the instrument after lasting for 30 minutes, taking out the reagent tank, wiping off external moisture, weighing, recording time and weight, and solving for average flow rate, wherein the minimum adjustable duty ratio is the percentage of the on-off delay of the two-way valve to the single sample injection time;
3.4) adjusting the duty ratio to be the maximum adjustable duty ratio, putting the reagent tank into water, powering off the instrument after lasting for 30 minutes, taking out the reagent tank, wiping off external moisture, weighing, recording time and weight, and solving for average flow rate; the sum of the maximum adjustable duty ratio and the minimum adjustable duty ratio is 1, and is mainly determined by the switching delay of the two-way valve and the single sample injection time;
3.5) adjusting the duty ratio to 1, putting the reagent tank into water, powering off the instrument after lasting for 30 minutes, taking out the reagent tank, wiping off external moisture, weighing, recording time and weight, and solving for average flow rate;
3.6) selecting two duty ratio measuring points between the minimum adjustable duty ratio and the maximum adjustable duty ratio, generally, the two duty ratio measuring points can approximately evenly 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;
and 3.7) carrying out curve fitting by using the average flow velocity of each duty ratio measuring point to obtain the functional relation of the average flow velocity to the duty ratio, wherein linear fitting is adopted.
Further, the step 4) comprises the following steps:
4.1) determining the number of calibration points required by calibration according to application requirements, wherein the number of the calibration points is 5 points at least;
4.2) determining the temperature of each calibration point according to the applied temperature range, and distributing the temperature evenly in the temperature range;
4.3) calibrating the relation between blank value channel background noise, water influence and temperature, turning off the LED, only keeping air in the detection channel, keeping the temperature at each calibration point for at least one hour, respectively recording the background noise of the main channel and the reference channel at each calibration point, and fitting a curve to obtain BElectric power+BWater (W)A curve;
4.4) calibrating the relation between the blank value channel LED and the temperature, turning on the LED, and detectingOnly air is reserved in the measuring channel, the temperature is kept at each calibration point for at least one hour, the signal values of the main channel and the reference channel are recorded at each calibration point respectively, and a curve is fitted to obtain CElectric power+CWater (W)The curve of (d);
4.5) applying Larobert's Law, blank value is BLight (es)＝B-BElectric power-BWater (W)Color rendering value of CLight (es)*ρTransforming＝C-CElectric power-CWater (W)；
Where B is the sample value of the blank channel, BElectric powerBackground noise of circuits being blank value channels, BWater (W)Background influence of water body of blank value channel, C sampling value of main light path of color rendering value channel, CElectric powerBackground noise of the circuit being the main light path of the color channel, CWater (W)Background influence of water body being main light path of color rendering value channel, CLight (es)Is the response of the luminous intensity of the light source LED at the receiving end, rhoTransformingIs the effect of the reaction between the substance to be measured in the sample and the chemical reagent.
Further, the step 5) comprises the following steps:
5.1) determining the number of fixed points, 5 points or 7 points according to the application condition;
5.2) determining the temperature of the calibration points, and evenly distributing the temperature within the 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 values of the standard solution at the highest temperature point and the lowest temperature point do not exceed the linear interval of the measurement range of the instrument;
5.4) heating the standard solution to the temperature of each calibration point in sequence, keeping the temperature for one hour, measuring and recording numerical values;
and 5.5) fitting by using the obtained data to obtain a curve formula.
Further, the step 6) comprises the following steps:
6.1) selecting a constant temperature point, and selecting normal temperature of 25 ℃ or 300 Kelvin;
6.2) selecting concentration calibration points in the target measuring range, at least selecting 5 points, wherein the concentrations of the other adjacent points except the concentration zero point satisfy 2 times of relationship;
6.3) placing the instrument, the reagent tank, the standard solution and the like into a constant temperature box, and keeping the constant 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, continuing for 1 hour, recording all blank values and color value data, then powering off the instrument, and replacing the reagent;
6.5) repeating the previous step under the condition of using standard solutions with different concentrations according to the sequence of the concentrations from small to large, and recording all data in the middle;
6.6) drawing a blank value curve and a color rendering value curve according to the time point sequence;
6.7) removing abnormal points which can be reasonably explained in the curve;
6.8) calculating the average values of each data interval of the blank value and the color rendering value in different concentration ranges, and representing the blank value and the color rendering value at each concentration point by the average values;
6.9) applying the average values of the blank value and the color rendering value to the Law of Lanberger to obtain the absorbance of each point;
6.10) fitting the relationship between the absorbance and the concentration of each point according to a linear relationship.
Further, the field calibration comprises the following steps:
1) closing the sample inlet, opening the standard solution port, and taking the liquid in the standard solution bag in the reagent tank as a test sample;
2) adjusting the sample injection speed of the standard solution to make the concentration of the standard solution be half of the full range of the instrument, and flushing the residual water sample on site for 10 minutes or until the sampling data is stabilized again;
3) starting a detection module, starting measurement, lasting for 30 minutes, and recording all data;
4) removing abnormal points which can be reasonably explained;
5) in the data smoothing stage, the blank value and the color rendering value are averaged to represent the blank value and the color rendering value of the concentration point;
6) applying Lanberg's law to obtain the absorbance of the spot;
7) and performing curve translation according to the relation between the half-range concentration point of the factory calibration curve and the on-site half-range concentration point data.
Advantageous effects
The invention provides a method which has the following beneficial effects:
1. the marine measuring instrument adopts the plunger pump and the electromagnetic valve as power, is convenient for measuring by using a flow injection method, has adjustable space and is convenient for calibration, thereby realizing more accurate profile measurement;
2. the T-shaped support is adopted, so that the positions of all the parts are relatively independent, and mutual interference is avoided;
3. when the calibration is carried out, the influence of main factors of measurement on a measurement result is avoided by 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 the calibration is carried out on site, the data can be corrected to a certain extent by a simple calibration method, and the measurement accuracy of the instrument is improved.
Drawings
FIG. 1 is a schematic structural view of the present invention;
FIG. 2 is a schematic structural view of the end cap of the present invention;
FIG. 3 is a schematic view of the structure within the housing of the present invention;
FIG. 4 is a schematic structural view of a stent of the present invention;
FIG. 5 is a schematic view of a single parameter fluid path of the present invention;
wherein 1 is the end cover, 2 is the casing, 3 is the electric interface, 4 is the inlet, 5 is reagent mouth, 6 is the mark liquid mouth, 7 is the liquid outlet, 8 is the modularization liquid way, 9 is detection module, 10 is the plunger pump, 11 is internal support, 12 is the main control board, 13 is the valve base, 14 is the solenoid valve, 15 is the seal pot.
The specific implementation mode is as follows:
the technical scheme of the invention is further specifically described by the following embodiments and the accompanying drawings.
Example 1
As shown in fig. 1-4, the cross-sectional marine measuring instrument includes an end cap 1, a housing 2, a main control board 12, a detection module 9, an internal support 11, a modular fluid path 8, a plunger pump 10, a solenoid valve 14, a valve base 13, a seal tank 15, a water pipe and a connector for connecting the fluid path, and an electric wire and a connector for electrical connection (not shown).
The end cover 1 is combined with the shell 2 to protect other components of the instrument and provide certain pressure resistance and watertight capacity for the components. In addition, the end cover is an external interface of the whole instrument, is provided with an electrical interface 3, a liquid inlet 4, a reagent port 5, a standard liquid port 6 and a liquid outlet 7, is electrically connected with the outside, has functions of a communication interface, sample sampling, reagent adding, waste liquid discharging and the like, and can be added with a pretreatment device at a sample sampling position according to needs to carry out pretreatment on a sample for removing various substances which influence measurement and are contained in the sample.
The main control board 12 is a core of the circuit control of the whole instrument and is used for realizing the control of each part of the bottom layer of the instrument. The instrument operation parameter setting is carried out by receiving an instruction from the upper computer, and after real-time sampling, data are stored to a designated position and transmitted according to requirements.
The detection module 9 is a technical key point of the whole instrument and is used for detecting a blank value and a color rendering value of a substance to be detected, and on the basis of the blank value and the color rendering value, the concentration of the substance to be detected can be calculated by applying the Law of Lanberger. When the detection module is applied to the single-parameter module, the detection module comprises a blank value channel and a color rendering value channel, the two channels are completely the same, and the specific function of each channel is determined by the water path connection mode.
The inner support 11 is used for placing all components of the instrument except the sealed tank, and places all the components on different sides of the inner support, so that water and electricity can be effectively isolated, and the instrument is easy to install and maintain.
The inside comparatively complicated liquid way that contains of modularization liquid way 8, compare with the liquid way of simply constituteing by the water pipe, modularization liquid way occupation space is less, and withstand voltage is higher to especially be fit for the more complicated condition of liquid way condition, like the multi-parameter. In addition, the design is flexible, and the requirements of various different measuring methods of the same parameter can be met without influencing other components of the instrument.
The plunger pump 10 is a sample introduction device of the instrument, is the most main power unit of the instrument, and can effectively control the sample introduction amount of a sample during single sample introduction by using different clock signals and setting different strokes. When the sample flow direction control device and the three-way electromagnetic valve are used together, the flow direction of the sample can be effectively controlled.
The solenoid valve 4 plays a role in controlling the liquid flow 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 act together to control the sample injection. The two-way solenoid valve acts alone, controls the circulation of reagent, through the duty cycle to two-way solenoid valve operating time, can effectively control the sample injection volume and the time of appearance of reagent.
The valve base 13 is an important base point for normal operation of the solenoid valve and the plunger pump, the solenoid valve and the plunger pump need to be fixed on a relatively stable solenoid valve base, and meanwhile, the specificity of the sample inlets of the solenoid valve and the plunger pump also determines that an independent solenoid valve base design needs to be carried out.
The seal pot 15 plays a certain sealing role, protects the plunger pump and the electromagnetic valve in the seal pot, and the seal pot is combined with the valve base for use, so that certain compression resistance protection and watertight protection are provided for the plunger pump and the electromagnetic valve, and the plunger pump and the electromagnetic valve can normally work under certain pressure.
The inside of instrument adopts T type supporting structure, looks down from the instrument end cover promptly, becomes the T type between the inside, in every frame, distributes and has screw hole and bar hole not of uniform size, and the benefit of doing so includes following several:
a plurality of sections can be formed, which is beneficial to the overall layout of accessories with different purposes;
the circuit part and the waterway part are effectively separated, so that mutual interference is avoided;
the installation and maintenance are easy, and the target component can be directly operated without influencing other parts;
each part in the frame can be finely adjusted to a certain degree;
is beneficial to the arrangement of water pipes and electric wires.
The liquid path can be divided into 3 parts according to the different components of the liquid, namely: sample portion, reagent portion, mixing portion. Wherein the sample portion has only the sample in flow communication, the reagent portion has only the reagent in flow communication, and the mixing portion has a mixture of the sample and the reagent in flow communication. The three parts are connected with each other on the modular liquid path.
The fluid path of a typical single parameter profile marine instrument should be as shown in figure 5.
The sample enters the instrument from a liquid inlet of the instrument end cover, flows through a blank value channel of the detection module after entering the instrument, and finally flows into a sample input port of the modularized liquid path.
Reagent enters the instrument from a reagent port of an instrument end cover, flows through the two-way valve after entering the instrument, and finally flows into a reagent input port of the modularized liquid path.
After the sample and the reagent flow into the modular liquid path, the sample and the reagent are mixed to perform chemical reaction, and after the mixed liquid flows out of the modular liquid path, the mixed liquid flows into the color rendering value channel of the detection module, then is sent into the plunger pump, and finally is discharged out of the instrument through the waste liquid port of the instrument end cover by the plunger pump.
Example 2
The instrument needs to be factory calibrated before factory shipment, and needs to be field calibrated when in use.
Factory calibration includes the following steps.
1) Application analysis
When the instrument is applied on site, various influence factors exist, and in a factory calibration stage, the following two points need to be considered emphatically: maximum concentration of the analyte and measurement resolution.
The maximum concentration of the object to be measured determines the minimum concentration of the reagent, and generally, the sample injection ratio of the sample and the reagent is further determined to meet the requirement that the reagent has enough quantity and cannot be less than the measuring range of the instrument.
Assuming that the maximum molarity of the target sample is a, 1 molecule of the analyte needs to react with n molecules of the reagent to generate the desired chromogenic substance according to the chemical reaction requirement, then the minimum molarity of the reagent should be n x a.
The measurement resolution refers to the distance moved by the instrument in one measurement period, the higher the resolution is, the denser the sampling points are, the higher the sampling rate of a single point is required, and then the sampling ratio of the sample and the reagent is considered, so that the minimum sampling rate of the reagent can be obtained.
Suppose that in an application, the instrument is moving at a velocity vMovable partThe working period is T, the measurement resolution is S, and the measurement resolution is
S＝vMovable part*T
Assuming that the duty ratio of the sampling time of the plunger pump in the whole working period is tau, the sampling amount of single sampling is V, and the sampling rate is VMixing deviceThen, then
V＝vMixing device*T*τ
Combining the two formulas to obtain
Therefore, under the condition that the movement speed of the instrument is constant, the higher the measurement resolution is, the smaller the measurement distance is, and the higher the sampling speed of the instrument is required to be.
Further, minimum sample introduction rate of instrument reagent
vMovable part＝vMixing device*n
2) Flow rate calibration
In the invention, the driving force of the sample and the reagent comes from the plunger pump, and the sample and the reagent divide the flow rate which can be provided by the plunger pump and share 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 sampling volume of the reagent can be adjusted by utilizing the conducting time of the two-way valve.
The reagent flow rate calibration can be performed as follows:
recording the initial weight of the reagent tank holding the reagent;
placing the instrument in the water, keeping it below the water surface;
adjusting the duty ratio to be the minimum adjustable duty ratio, putting the reagent tank into water, powering off the instrument after lasting for 30 minutes, taking out the reagent tank, wiping off external moisture, weighing, recording time and weight, and solving the average flow rate; the minimum adjustable duty ratio is the percentage of the on-off delay of the two-way valve in the single sample injection time;
adjusting the duty ratio to be the maximum adjustable duty ratio, putting the reagent tank into water, powering off the instrument after lasting for 30 minutes, taking out the reagent tank, wiping off external moisture, weighing, recording time and weight, and solving the average flow rate; the sum of the maximum adjustable duty ratio and the minimum adjustable duty ratio is 1, and is mainly determined by the switching delay of the two-way valve and the single sample injection time;
adjusting the duty ratio to be 1, putting the reagent tank into water, powering off the instrument after lasting for 30 minutes, taking out the reagent tank, wiping off external moisture, weighing, recording time and weight, and solving the average flow rate;
selecting two duty ratio measurement points between the minimum adjustable duty ratio and the maximum adjustable duty ratio, generally, the two duty ratio measurement points can approximately 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;
performing curve fitting by using the average flow velocity of each duty ratio measurement point to obtain a functional relation between the average flow velocity and the duty ratio, generally using linear fitting;
in most cases, the sample injection speed required by the reagent and the sample is greatly different, the sample injection speed required by the reagent is far less 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 duty ratio of the reagent can be adjusted according to a larger step length, so that the corresponding sample and reagent sampling speed proportion can be achieved.
3) Calibration of LED light source
In the invention, the light source receiving end receives the photoelectric signal and samples the photoelectric signal to be expressed in the form of digital quantity, all variables are digital quantity without unit, and if necessary, the relation between the required unit and the digital quantity can be derived automatically.
The following relationship is satisfied at the blank value channel:
B＝Belectric power＋BWater (W)＋BLight (es)
Wherein, B is a sampling value of a blank value channel; b isElectric powerThe background noise of the circuit that is the blank value channel; b isWater (W)The background influence of the water body of the blank value channel mainly reflects the influence of factors such as turbidity, fluorescence and the like of the water body, and the value of the background influence is far smaller than that of B in the application of a spectrophotometer methodLight (es)Generally, the noise can be ignored, and when the influence is large and cannot be ignored, the noise can be used as a fixed value for calculation and is merged into circuit noise during calculation; b isLight (es)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＝Celectric power+CWater (W)+CLight (es)*ρTransforming
Wherein, C is a sampling value of a main optical path of a color rendering value channel; cElectric powerIs the background noise of the circuit of the main light path of the color rendering channel; cWater (W)The background influence of the water body of the main light path of the color rendering value channel; cLight (es)The response of the luminous intensity of the light source LED at the receiving end; rhoTransformingThe influence is generated after the substance to be detected in the sample reacts with the chemical reagent, the intensity of the light beam is reduced, and the higher the concentration is, the more remarkable the reduction is.
In the invention, the relation between the LED luminous intensity and the temperature needs to be calibrated before the instrument is used, so that a basis is provided for later data correction.
The specific operation is as follows:
determining the number of calibration points required by calibration according to application requirements, and generally proposing 7 points or 9 points in a laboratory, and 5 points at least;
determining the temperature of each index point according to the temperature range of the application, generally, it is recommended to distribute equally within the temperature range;
calibrating the relationship between blank channel background noise, water effects and temperature: turning off the LED, keeping only air in the detection channel, keeping constant temperature at each calibration point for at least one hour, recording background noises of the main channel and the reference channel at each calibration point respectively, fitting a curve,to obtain BElectric power+BWater (W)A curve;
calibrating the relationship between the blank channel LED and the temperature: opening the LED, only reserving air in the detection channel, keeping the temperature of each calibration point for at least one hour, respectively recording signal values of the main channel and the reference channel at each calibration point, and fitting a curve to obtain CElectric power+CWater (W)The curve of (d);
applying Law of Lanberel, blank value BLight (es)＝B-BElectric power-BWater (W)Color rendering value of CLight (es)*ρTransforming＝C-CElectric power-CWater (W)；
4) Calibration of chemical reaction efficiency
In the invention, the influence of temperature on the chemical reaction can also be corrected by a calibration method, and the specific flow is as follows:
determining the number of fixed points, 5 points or 7 points according to the application condition;
determining the temperature of the calibration points, generally evenly distributing in a temperature range, and recommending that the distance between the temperature points is not less than 5 ℃;
selecting a certain concentration of standard solution, wherein the test values of the standard solution at the highest temperature point and the lowest temperature point do not exceed the linear interval of the measurement range of the instrument;
heating the standard solution to the temperature of each calibration point in sequence, keeping the temperature for one hour, and measuring and recording 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 generally, the temperature sensor is placed in the liquid path before the inlet of the detection module.
5) Concentration calibration
In the present invention, the predominantly applied Schwarburger's law, according to the previous procedure, has already calibrated the effect of temperature on the measurement results, and concentration calibration is performed below at constant temperature.
The concentration calibration method comprises the following steps:
selecting a constant temperature point, suggesting a normal temperature, i.e. 25 ℃ or 300 kelvin;
selecting concentration calibration points in the target measuring range, and suggesting to select 5 points, wherein the concentrations of other adjacent points except the concentration zero point satisfy a 2-time relationship;
placing the instrument, the reagent tank, the standard solution and the like into a constant temperature box, and keeping the constant temperature at a constant temperature point for 1 hour;
taking a standard solution with the concentration of 0 as a sample, starting measurement, lasting for 1 hour, recording all blank value and color value data, then 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 standard solutions with different concentrations, and recording all data in the middle;
drawing a blank value curve and a color rendering value curve according to the time point sequence;
removing abnormal points in the curve which can be reasonably explained, such as obvious points containing bubbles, false data points caused by startup and shutdown, data fluctuation in the preheating stage of the LED and the like;
averaging the blank values and the color values of the data intervals in different concentration ranges, and representing the blank values and the color values of the concentration points by the average values;
obtaining the absorbance of each point by applying the blank values and the mean value of the color rendering values and applying the Lanberg law;
fitting the relationship between the absorbance and the concentration of each point according to a linear relationship;
in field application, various parameters of the instrument can drift along with the combined action of the service time and various stresses, and the accuracy of the instrument is seriously influenced sometimes, so that calibration needs to be carried out again for correction, and calibration needs to be carried out on the field.
The field calibration can be performed as follows.
Closing the sample inlet, opening the standard solution port, and taking the liquid in the standard solution bag in the reagent tank as a test sample;
adjusting the sample injection speed of the standard solution through software to enable the concentration of the standard solution to be half of the full range of the instrument, flushing the residual water sample on site for 10 minutes, or until the sampling data is stabilized again;
starting the detection module, starting the measurement, lasting for 30 minutes, and recording all data;
removing abnormal points which can be reasonably explained, such as obvious points containing bubbles, false data points caused by startup and shutdown, data fluctuation in the LED preheating stage and the like;
calculating an average value of the blank value and the color value in the data smoothing stage, wherein the average value represents the blank value and the color value of the concentration point;
applying Lanberg's law to obtain the absorbance at this point;
according to the relation between the first half-range concentration point and the second half-range concentration point data of the original factory calibration curve, curve translation is carried out, namely
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The utility model provides a section marine surveying instrument, includes casing and end cover, its characterized in that: the bottom of the interior of the shell is provided with a seal pot, a plunger pump and an electromagnetic valve are arranged in the seal pot, the plunger pump and the electromagnetic valve are fixedly connected with the bottom surface of a valve base at the top of the seal pot, a T-shaped support is arranged on the top surface of the valve base, a modular liquid path, a detection module and a main control board are arranged on the T-shaped support, the top of the support is an end cover, the main control board is electrically connected with the modular liquid path, the detection module, the plunger pump and the electromagnetic valve, and an inlet, a reagent port, a liquid outlet, a standard liquid port and an electrical interface are arranged on the.
2. A profile marine measurement instrument according to claim 1, wherein: the liquid path in the modularization 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.
3. A method of calibrating a cross-sectional marine surveying instrument as claimed in any one of claims 1 to 2, characterized by: the method comprises factory calibration and field calibration, wherein the factory calibration comprises the following steps:
1) determining the minimum concentration of the reagent according to the maximum concentration of the sample;
2) determining the minimum sample introduction 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.
4. The method for calibrating the profile marine measuring instrument according to claim 3, characterized in that: the maximum molarity of the sample in step 1) is a, wherein 1 molecule of the substance to be detected needs to react with n molecules of the reagent, and the lowest molarity of the reagent should be n x a.
5. The method for calibrating the profile marine measuring instrument according to claim 3, characterized in that: the minimum sample introduction rate of the reagent in the step 2) is
Wherein the instrument has a speed of movement vMovable partThe sampling volume 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 measured substance molecule needs to react with n reagent molecules.
6. The method for calibrating the profile marine measuring instrument according to claim 3, characterized in that: the step 3) comprises the following steps:
3.1) recording the initial weight of the reagent tank storing the reagent;
3.2) putting the instrument into water and keeping the instrument below the water surface;
3.3) adjusting the duty ratio to be the minimum adjustable duty ratio, putting the reagent tank into water, powering off the instrument after lasting for 30 minutes, taking out the reagent tank, wiping off external moisture, weighing, recording time and weight, and solving for average flow rate, wherein the minimum adjustable duty ratio is the percentage of the on-off delay of the two-way valve to the single sample injection time;
3.4) adjusting the duty ratio to be the maximum adjustable duty ratio, putting the reagent tank into water, powering off the instrument after lasting for 30 minutes, taking out the reagent tank, wiping off external moisture, weighing, recording time and weight, and solving for average flow rate; the sum of the maximum adjustable duty ratio and the minimum adjustable duty ratio is 1, and is mainly determined by the switching delay of the two-way valve and the single sample injection time;
3.5) adjusting the duty ratio to 1, putting the reagent tank into water, powering off the instrument after lasting for 30 minutes, taking out the reagent tank, wiping off external moisture, weighing, recording time and weight, and solving for average flow rate;
3.6) selecting two duty ratio measuring points between the minimum adjustable duty ratio and the maximum adjustable duty ratio, wherein the two duty ratio measuring points can approximately evenly 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;
and 3.7) carrying out curve fitting by using the average flow velocity of each duty ratio measuring point to obtain the functional relation of the average flow velocity to the duty ratio, wherein linear fitting is adopted.
7. The method for calibrating the profile marine measuring instrument according to claim 3, characterized in that: the step 4) comprises the following steps:
4.1) determining the number of calibration points required by calibration according to application requirements, wherein the number of the calibration points is 5 points at least;
4.2) determining the temperature of each calibration point according to the applied temperature range, and distributing the temperature evenly in the temperature range;
4.3) calibrating the blank value channel background noise,The relation between the water influence and the temperature is closed, only air is reserved in the detection channel, the temperature is kept at each calibration point for at least one hour, the background noise of the main channel and the background noise of the reference channel are recorded at each calibration point respectively, and a curve is fitted to obtain BElectric power+BWater (W)A curve;
4.4) calibrating the relation between the blank value channel LED and the temperature, turning on the LED, only reserving air in the detection channel, keeping the temperature of each calibration point for at least one hour, respectively recording the signal values of the main channel and the reference channel at each calibration point, and fitting a curve to obtain CElectric power+CWater (W)The curve of (d);
4.5) applying Larobert's Law, blank value is BLight (es)＝B-BElectric power-BWater (W)Color rendering value of CLight (es)*ρTransforming＝C-CElectric power-CWater (W)；
Where B is the sample value of the blank channel, BElectric powerBackground noise of circuits being blank value channels, BWater (W)Background influence of water body of blank value channel, C sampling value of main light path of color rendering value channel, CElectric powerBackground noise of the circuit being the main light path of the color channel, CWater (W)Background influence of water body being main light path of color rendering value channel, CLight (es)Is the response of the luminous intensity of the light source LED at the receiving end, rhoTransformingIs the effect of the reaction between the substance to be measured in the sample and the chemical reagent.
8. The method for calibrating the profile marine measuring instrument according to claim 3, characterized in that: the step 5) comprises the following steps:
5.1) determining the number of fixed points, 5 points or 7 points according to the application condition;
5.2) determining the temperature of the calibration points, and evenly distributing the temperature within the 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 values of the standard solution at the highest temperature point and the lowest temperature point do not exceed the linear interval of the measurement range of the instrument;
5.4) heating the standard solution to the temperature of each calibration point in sequence, keeping the temperature for one hour, measuring and recording numerical values;
and 5.5) fitting by using the obtained data to obtain a curve formula.
9. The method for calibrating the profile marine measuring instrument according to claim 3, characterized in that: the step 6) comprises the following steps:
6.1) selecting a constant temperature point, and selecting normal temperature of 25 ℃ or 300 Kelvin;
6.2) selecting the number of concentration calibration points in the target measuring range, at least selecting 5 points, and satisfying 2 times of relationship among the concentrations of other adjacent points except the zero point of the concentration;
6.3) placing the instrument, the reagent tank, the standard solution and the like into a constant temperature box, and keeping the constant 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, continuing for 1 hour, recording all blank values and color value data, then powering off the instrument, and replacing the reagent;
6.5) repeating the previous step under the condition of using standard solutions with different concentrations according to the sequence of the concentrations from small to large, and recording all data in the middle;
6.6) drawing a blank value curve and a color rendering value curve according to the time point sequence;
6.7) removing abnormal points which can be reasonably explained in the curve;
6.8) calculating the average values of each data interval of the blank value and the color rendering value in different concentration ranges, and representing the blank value and the color rendering value at each concentration point by the average values;
6.9) applying the average values of the blank value and the color rendering value to the Law of Lanberger to obtain the absorbance of each point;
6.10) fitting the relationship between the absorbance and the concentration of each point according to a linear relationship.
10. The method for calibrating the profile marine measuring instrument according to claim 3, characterized in that: the field calibration comprises the following steps:
1) closing the sample inlet, opening the standard solution port, and taking the liquid in the standard solution bag in the reagent tank as a test sample;
2) adjusting the sample injection speed of the standard solution to make the concentration of the standard solution be half of the full range of the instrument, and flushing the residual water sample on site for 10 minutes or until the sampling data is stabilized again;
3) starting a detection module, starting measurement, lasting for 30 minutes, and recording all data;
4) removing abnormal points which can be reasonably explained;
5) in the data smoothing stage, the blank value and the color rendering value are averaged to represent the blank value and the color rendering value of the concentration point;
6) applying Lanberg's law to obtain the absorbance of the spot;
7) and performing curve translation according to the relation between the half-range concentration point of the factory calibration curve and the on-site half-range concentration point data.
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| CN116608887A (en) * | 2023-07-17 | 2023-08-18 | 山东科技大学 | Disposable ocean current profiler test calibration device and method |
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