CN119165036A - A method for detecting mercury content in solid waste - Google Patents
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- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 191
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims abstract description 189
- 238000000034 method Methods 0.000 title claims abstract description 108
- 239000002910 solid waste Substances 0.000 title claims abstract description 50
- 230000004044 response Effects 0.000 claims abstract description 139
- 238000001514 detection method Methods 0.000 claims abstract description 50
- 230000029087 digestion Effects 0.000 claims abstract description 32
- 238000000835 electrochemical detection Methods 0.000 claims abstract description 25
- 238000004458 analytical method Methods 0.000 claims abstract description 24
- 238000005070 sampling Methods 0.000 claims abstract description 7
- 238000012216 screening Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 41
- 238000000120 microwave digestion Methods 0.000 claims description 35
- 239000012488 sample solution Substances 0.000 claims description 34
- 238000004422 calculation algorithm Methods 0.000 claims description 31
- 238000012937 correction Methods 0.000 claims description 25
- RWQNBRDOKXIBIV-UHFFFAOYSA-N thymine Chemical compound CC1=CNC(=O)NC1=O RWQNBRDOKXIBIV-UHFFFAOYSA-N 0.000 claims description 18
- 239000000523 sample Substances 0.000 claims description 17
- 238000012360 testing method Methods 0.000 claims description 17
- 238000004364 calculation method Methods 0.000 claims description 11
- 238000005259 measurement Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 108091023037 Aptamer Proteins 0.000 claims description 9
- 229940113082 thymine Drugs 0.000 claims description 9
- 238000005457 optimization Methods 0.000 claims description 8
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- 239000012086 standard solution Substances 0.000 claims description 7
- 238000011084 recovery Methods 0.000 claims description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
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- 238000012549 training Methods 0.000 claims description 3
- 230000007613 environmental effect Effects 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 230000006378 damage Effects 0.000 description 3
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- 230000009286 beneficial effect Effects 0.000 description 2
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- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 108091008102 DNA aptamers Proteins 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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Abstract
The invention relates to the field of mercury content detection, in particular to a method for detecting mercury content in solid waste. The method comprises the steps of obtaining a solid waste sample, crushing and screening the solid waste sample, obtaining a solution to be detected through random sampling and digestion treatment, obtaining effective response current of the solution to be detected through an electrochemical detection method, obtaining mercury content of the solution to be detected according to a standard relation curve of mercury content of the effective response current, marking the mercury content as first mercury content, obtaining characteristic signals related to the mercury content of the solution to be detected, obtaining a predicted value of the mercury content through a mercury content prediction model, marking the predicted value as second mercury content, and obtaining third mercury content through numerical analysis of the first mercury content and the second mercury content. The accuracy and the efficiency of detection are improved, and the rapid and accurate detection of the mercury content in the solid waste is realized.
Description
Technical Field
The invention relates to the field of mercury content detection, in particular to a method for detecting mercury content in solid waste.
Background
The detection of mercury content in solid waste is always an important environmental control link, and mercury is a toxic heavy metal, so that the mercury has potential long-term harm to human health and ecosystems. In particular, the solid waste produced after the current industrial production contains a certain amount of mercury, and if the mercury content in the solid waste is not accurately detected and is subjected to landfill treatment, serious pollution and harm are caused to the local environment. Therefore, the method accurately and efficiently detects the mercury content in the solid waste, ensures that the mercury content accords with national and international environmental standards, and is an important measure for ensuring environmental safety.
Traditional mercury detection methods, such as cold atomic absorption spectrometry, atomic fluorescence spectrometry and the like, have higher accuracy, but tend to be complex in operation, take longer time, require professional laboratory environments and expensive instruments and equipment, and are not beneficial to quickly screening the mercury content in the solid waste.
Therefore, the accuracy and the efficiency of detection are further improved, the rapid and accurate detection of the mercury content in the solid waste is realized, timely and reliable detection data are provided for enterprises, the mercury content in the solid waste treatment process is ensured to meet the environmental protection standard, and the environmental pollution risk is effectively prevented and controlled. It is particularly important to adopt a rapid and efficient method for detecting the mercury content of the solid waste.
Disclosure of Invention
(1) Technical problem to be solved
The invention aims to provide a method for detecting mercury content in solid waste, which aims to solve the problems of insufficient simplicity and high efficiency in mercury content detection.
(2) Technical proposal
To achieve the above object, in one aspect, the present invention provides a method for detecting mercury content in solid waste, the method comprising:
s1, obtaining a solid waste sample, crushing and screening according to a preset particle size to obtain a first sample, and randomly sampling and digesting the first sample to obtain a solution to be tested.
S2, obtaining effective response current of the solution to be detected through an electrochemical detection method, obtaining mercury content of the solution to be detected according to a standard relation curve of mercury content of the effective response current, and marking the mercury content as first mercury content, wherein an electrochemical sensor used by the electrochemical detection method comprises a mercury-specific sensitive material.
And S3, acquiring a characteristic signal related to the mercury content of the solution to be detected, obtaining a predicted value of the mercury content by using the characteristic signal through a mercury content prediction model, and marking the predicted value as a second mercury content.
And S4, obtaining third mercury content by numerical analysis of the first mercury content and the second mercury content, and outputting the third mercury content in a text or graphic form.
Further, the method for obtaining the mercury content of the solution to be detected according to the standard relation curve of the mercury content and marking the mercury content as the first mercury content comprises the following steps:
And obtaining a group of response currents through an electrochemical detection method, analyzing the group of response currents through normal distribution, obtaining the response currents in a preset confidence interval, marking the response currents as reliable response currents, and calculating the reliable response currents through average values to obtain effective response currents.
Standard solution with known mercury content is obtained, standard response current is obtained through an electrochemical detection method, and a standard relation curve is obtained through least square fitting of the relation between the standard response current and the mercury content.
Further, the method for obtaining a set of response currents from the set of detection sample solutions through an electrochemical detection method comprises the following steps:
the set of test sample solutions is noted as The response current corresponding to the group of detection sample solutions is recorded asObtaining a detection sample solutionThe detection sample solutionObtaining a response current by applying a preset voltageThe preset voltage is the detection voltage of the electrochemical detection method.
Subjecting the test sample solution toAccording to a preset voltage and a preset detection time interval, measuring to obtain M groups of corrected response currents, obtaining the deviation degree of the M groups of corrected response currents by adopting deviation difference analysis, and obtaining the response current by adopting a mean value algorithm from the response currents with the deviation degree smaller than a preset deviation threshold value。
Further, the M groups of corrected response currents adopt deviation difference analysis to obtain deviation degree, and the response currents with the deviation degree smaller than a preset deviation threshold value adopt a mean value algorithm to obtain response currentsThe method of (1) comprises:
The standard response currents of the standard solution at different temperatures when different detection voltages are applied are obtained, and the standard response currents are fitted to obtain temperature correction curves of the different detection voltages.
And acquiring a temperature correction curve corresponding to the preset voltage, and calculating correction coefficients of different temperatures and the target temperature according to the temperature correction curve.
Obtaining a test sample solutionThe method comprises the steps of measuring the actual measured temperature of response current, obtaining a corresponding correction coefficient according to the actual measured temperature, and correcting the response current through the correction coefficient to obtain corrected response current。
Subjecting the test sample solution toThe measured M sets of corrected response currents are recorded asObtaining a reference response current through a mean value calculation methodThe reference response currentObtaining the deviation degree of the M groups of correction response currents through deviation analysisThe degree of deviationThe calculation formula of (2) is as follows:
;
Will correct the response current And reference response currentIs smaller than the deviation degreeIs a correction response current of (a)Reserve and record as qualified response currentAnd passing the qualified response currentObtaining response current through mean value calculation method。
Further, the method further comprises:
Obtaining a preset voltage test sample solution, determining a preset voltage according to a scanning algorithm, obtaining an adjustment voltage according to an initial voltage, an adjustment time interval and an adjustment voltage difference value preset by the scanning algorithm, obtaining a response current corresponding to the adjustment voltage, drawing a voltage current curve, obtaining an adjustment voltage corresponding to a peak response current of the voltage current curve, and recording the adjustment voltage as the preset voltage.
Further, the method for obtaining the characteristic signal of the solution to be detected related to the mercury content, and obtaining the predicted value of the mercury content from the characteristic signal through a mercury content prediction model and marking the predicted value as the second mercury content comprises the following steps:
the characteristic signals comprise effective response current of the solution to be detected, corresponding preset voltage and types and proportions of solid wastes for preparing the solution to be detected;
The method comprises the steps of obtaining the type, the proportion, the effective response current and the corresponding preset voltage of the solid waste detected by the historical mercury content, wherein the mercury content prediction model is used for establishing the mapping relation between the type, the proportion, the effective response current and the corresponding preset voltage of the solid waste and the mercury content through a deep learning algorithm.
Further, the method for obtaining the third mercury content by numerical analysis of the first mercury content and the second mercury content comprises the following steps:
At the first mercury content And a second mercury content ofWhen the absolute percentage difference of the first mercury content and the second mercury content is smaller than a preset difference threshold value, obtaining a third mercury content through a mean algorithmUpdating and training a mercury content prediction model;
At the first mercury content And a second mercury content ofWhen the absolute percentage difference of the mercury is larger than a preset difference threshold value, the mercury content is calculatedRe-detecting;
The mean value algorithm adopts a linear weighting algorithm to obtain the third mercury content First mercury contentAnd a second mercury content ofThe weight coefficients of (2) are respectively preset、And (2) andThird mercury contentThe method comprises the following steps:。
Further, the method for obtaining the solution to be measured by randomly sampling and digesting the first sample comprises the following steps:
the microwave digestion process adopts a microwave digestion method, and microwave digestion parameters are obtained through an orthogonal design optimization method according to a preset microwave digestion target, wherein the preset microwave digestion target comprises digestion efficiency and recovery rate, and the microwave digestion parameters comprise digestion temperature, digestion time, digestion agent types and consumption;
Obtaining an analysis result of the microwave digestion parameters through a data analysis method, and obtaining a microwave digestion parameter corresponding to the maximum value of the analysis result to be recorded as an optimal microwave digestion parameter;
carrying out digestion treatment according to the optimal microwave digestion parameters, and acquiring temperature parameters and pressure parameters in the digestion treatment process by a real-time monitoring method; and adjusting the optimal microwave digestion parameters through an optimization algorithm according to the temperature parameters and the pressure parameters.
Further, the electrochemical detection method uses an electrochemical sensor comprising a mercury-specific sensitive material, and the method comprises:
The sensitive material is an aptamer rich in thymine, and the electrochemical sensor is obtained by connecting the aptamer rich in thymine on the surface of the nano-porous gold through a self-assembly method.
(3) Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
the effective response current of the solution to be measured can be accurately obtained by combining the electrochemical detection method with the voltage scanning algorithm and the temperature correction curve, and the measurement error caused by voltage and temperature change is effectively reduced.
The electrochemical detection and the model prediction are combined, and the results of the electrochemical detection and the model prediction are synthesized through numerical analysis, so that the detection value is verified, the number of repeated experiments is reduced, the detection accuracy is improved, and the environmental safety is ensured.
Drawings
FIG. 1 is a block flow diagram of a method for detecting mercury content in solid waste according to an embodiment of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Before the example, the application scenario of the present invention needs to be described, and with the rapid development of cities, industries and the like, a large amount of hazardous waste is generated, so that the large amount of hazardous comprehensive waste needs to be disposed in time. According to the conventional practice of the solid waste pollution control method of clause 88 and hazardous waste industry, solid waste includes liquids in containers and hazardous non-solid waste. Wherein, a great amount of slag is generated after the rotary furnace incinerator process of the hazardous waste comprehensive disposal system, and the solid waste of the slag is subjected to heavy metal content detection, wherein mercury content detection is included, because mercury is a toxic heavy metal, has potential long-term hazard to human health and ecosystems, and can pollute the environment if being directly buried. Therefore, the mercury content in the solid waste needs to be detected, if the detection reaches the standard, the solid waste can be buried according to the environmental protection standard, and if the detection does not reach the standard, further treatment, such as stabilization or solidification technology of the solid waste by adopting cement, fly ash or lime and the like as a solidifying agent, is required to react with mercury in the solid waste to form indissolvable or stable compounds, and the toxicity and mobility of the indissolvable or stable compounds are reduced to achieve the purposes of stabilization and innocuity.
Example as shown in fig. 1, the present example provides a method for detecting mercury content in solid waste, the method comprising:
S1, obtaining a solid waste sample, crushing and screening according to a preset particle size to obtain a first sample, randomly sampling and digesting the first sample to obtain a solution to be tested, wherein the incinerated slag, namely the solid waste, has larger and uneven particles, so that a certain amount of solid waste is sampled from different areas of the site slag, crushed by a crusher, filtered by a mesh screen to obtain grinding powder meeting the requirements, the grinding powder is placed in a glass dish, uniformly mixed, randomly sampled to obtain quantitative grinding powder, and the quantitative grinding powder is prepared into a solution and digested by a microwave oven. The microwave digestion is to directly penetrate the substance through electromagnetic waves of 300-300000 MHz, and generate a heat effect when the microwaves reach, so that organic matters are decomposed, and the digestion of the substance is realized. The purpose of digestion is to break down the solid sample, converting it into a solution form that can be analyzed.
S2, obtaining effective response current of the solution to be detected through an electrochemical detection method, obtaining mercury content of the solution to be detected according to a standard relation curve of mercury content of the effective response current, and marking the mercury content as first mercury content, wherein an electrochemical sensor used by the electrochemical detection method comprises a mercury-specific sensitive material, and the embodiment adopts nano porous gold as a carrier material of the electrochemical sensor. The sensitive material is an aptamer rich in thymine, and the aptamer can be combined with mercury ions in a solution with high selectivity, so that the sensitive material has good sensitivity and selectivity. Substituting the response current of the solution to be measured into a standard relation curve, and obtaining the mercury content of the solution to be measured through interpolation calculation.
S3, obtaining a characteristic signal related to mercury content of the solution to be detected, obtaining a predicted value of mercury content by a mercury content prediction model through the characteristic signal, and marking the predicted value as second mercury content;
And S4, obtaining third mercury content by numerical analysis of the first mercury content and the second mercury content, and outputting the third mercury content in a text or graphic form.
Further, the method for obtaining the mercury content of the solution to be detected according to the standard relation curve of the mercury content and marking the mercury content as the first mercury content comprises the following steps:
When the PH value of the solution to be detected is obtained and is within the designed PH value detection range of the electrochemical sensor, a group of detection sample solutions are obtained according to the preset detection sample quantity by the solution to be detected, a group of response currents are obtained by the group of detection sample solutions through an electrochemical detection method, the group of response currents are analyzed through normal distribution, the response currents in a preset confidence interval are obtained and are recorded as reliable response currents, the reliable response currents are calculated through mean value to obtain effective response currents, the performance of the electrochemical sensor can be influenced by the PH value of the solution, and the PH value exceeding the design range of the electrochemical sensor can lead to inaccurate measurement results or damage of the sensor. Therefore, the electrochemical sensor has larger and more accurate measured value of response current in the optimal PH value detection range. The "preset number of samples to be tested" is to take out a plurality of samples from the solution to be tested for testing in order to increase the reliability of the measurement result and reduce accidental errors. Because instrument errors, operation errors and the like exist in the measurement process, the obtained set of response current values can show a certain distribution rule, and are normally distributed. A pre-set confidence interval (e.g., 95% confidence interval) is determined by statistical analysis, and the response current values within this interval are considered reliable.
Standard solution with known mercury content is obtained, standard response current is obtained through an electrochemical detection method, and a standard relation curve is obtained through least square fitting of the relation between the standard response current and the mercury content. Standard solutions of known mercury content used in this example were purchased at standard substance centers.
Further, the method for obtaining a set of response currents from the set of detection sample solutions through an electrochemical detection method comprises the following steps:
the set of test sample solutions is noted as The response current corresponding to the group of detection sample solutions is recorded asObtaining a detection sample solutionThe detection sample solutionObtaining a response current by applying a preset voltageThe preset voltage is the detection voltage of the electrochemical detection method.
Subjecting the test sample solution toAccording to a preset voltage and a preset detection time interval, measuring to obtain M groups of corrected response currents, obtaining the deviation degree of the M groups of corrected response currents by adopting deviation difference analysis, and obtaining the response current by adopting a mean value algorithm from the response currents with the deviation degree smaller than a preset deviation threshold value. The preset time interval is determined according to the response time of the detection system.
Further, the M groups of corrected response currents adopt deviation difference analysis to obtain deviation degree, and the response currents with the deviation degree smaller than a preset deviation threshold value adopt a mean value algorithm to obtain response currentsThe method of (1) comprises:
The method comprises the steps of obtaining standard response currents of standard solutions at different temperatures when different detection voltages are applied, fitting the standard response currents to obtain temperature correction curves when different detection voltages are obtained, forming data points related to the relation among the voltages, the temperatures and the response currents through measurement data obtained through measurement, and fitting the data points by using a mathematical method to obtain a relation curve of the response currents along with the changes of the temperatures and the voltages.
The temperature of the detected sample solution is recorded as the target temperature when the measurement is not carried out, a temperature correction curve corresponding to the preset voltage is obtained, and correction coefficients of different temperatures and the target temperature are calculated according to the temperature correction curve;
Obtaining a test sample solution The method comprises the steps of measuring the actual measured temperature of response current, obtaining a corresponding correction coefficient according to the actual measured temperature, and correcting the response current through the correction coefficient to obtain corrected response current;
Subjecting the test sample solution toThe measured M sets of corrected response currents are recorded asObtaining a reference response current through a mean value calculation methodThe reference response currentObtaining the deviation degree of the M groups of correction response currents through deviation analysisThe degree of deviationThe calculation formula of (2) is as follows:
;
Will correct the response current And reference response currentIs smaller than the deviation degreeIs a correction response current of (a)Reserve and record as qualified response currentAnd passing the qualified response currentObtaining response current through mean value calculation method. The absolute difference value is a corrected response currentSubtracting the reference response currentIs the absolute value of (c). The mean value calculation method adopts an arithmetic average method to calculate the response current。
Further, the method further comprises:
Obtaining a preset voltage test sample solution, determining a preset voltage according to a scanning algorithm, obtaining an adjustment voltage according to an initial voltage, an adjustment time interval and an adjustment voltage difference value preset by the scanning algorithm, obtaining a response current corresponding to the adjustment voltage, drawing a voltage current curve, obtaining an adjustment voltage corresponding to a peak response current of the voltage current curve, and recording the adjustment voltage as the preset voltage. The preset voltage is obtained by extracting the preset voltage test sample solution from the solution to be tested, and the M groups of corrected response currents are obtained by measuring each detection sample solution by adopting the obtained preset voltage, so that the peak response currents can be reduced to be redetermined by adopting a scanning algorithm in each measurement, and the detection voltages corresponding to the peak response currents of the same group of sample solutions are basically consistent, and the measurement errors caused by different voltages can be reduced by adopting the same detection voltage for measurement.
Further, the method for obtaining the characteristic signal of the solution to be detected related to the mercury content, and obtaining the predicted value of the mercury content from the characteristic signal through a mercury content prediction model and marking the predicted value as the second mercury content comprises the following steps:
the characteristic signals comprise effective response current of the solution to be detected, corresponding preset voltage and types and proportions of solid wastes for preparing the solution to be detected;
The method comprises the steps of obtaining the type, the proportion, the effective response current and the corresponding preset voltage of the solid waste detected by the historical mercury content, wherein the mercury content prediction model is used for establishing the mapping relation between the type, the proportion, the effective response current and the corresponding preset voltage of the solid waste and the mercury content through a deep learning algorithm. Different kinds of incinerated substances, which themselves contain different heavy metals and contents, are pretreated before incineration, and have different kinds of incinerated substance data and different kinds of incineration proportion data. And (3) combining the data of the types and the proportion of the burned objects with the data of the detected mercury content, and establishing a mercury content prediction model through a neural network algorithm. The kinds and proportions of the solid wastes are classified and counted before the wastes are incinerated, so that the kinds and proportions of the finally produced waste residues can be obtained based on the statistical data of the incineration. For example, the waste may comprise metal chips, plastic, glass, electronic equipment debris that may contain mercury, and the like. The proportion of each component may be important for predicting mercury content, as mercury may concentrate in certain specific types of waste.
Further, the method for obtaining the third mercury content by numerical analysis of the first mercury content and the second mercury content comprises the following steps:
At the first mercury content And a second mercury content ofWhen the absolute percentage difference of the first mercury content and the second mercury content is smaller than a preset difference threshold value, obtaining a third mercury content through a mean algorithmAnd when the absolute percentage difference is smaller than a preset difference threshold, the mercury content is obtained more accurately, so that the corresponding characteristic signals are used as training data to update or optimize the mercury content prediction model, the accuracy and generalization capability of the model are improved, and the mercury content of other waste samples can be predicted more accurately.
At the first mercury contentAnd a second mercury content ofWhen the absolute percentage difference of the mercury is larger than a preset difference threshold value, the mercury content is calculatedRe-detecting;
The mean value algorithm adopts a linear weighting algorithm to obtain the third mercury content First mercury contentAnd a second mercury content ofThe weight coefficients of (2) are respectively preset、And (2) andThird mercury contentThe method comprises the following steps: . The weight of the detection result by the electrochemical sensor is larger than that of the mercury content prediction model.
Further, the method for obtaining the solution to be measured by randomly sampling and digesting the first sample comprises the following steps:
The digestion treatment adopts a microwave digestion method, microwave digestion parameters are obtained through an orthogonal design optimization method according to a preset microwave digestion target, the preset microwave digestion target comprises digestion efficiency and recovery rate, the microwave digestion parameters comprise digestion temperature, digestion time, digestion agent types and consumption, and the microwave digestion method is used for decomposing a solid sample and converting the solid sample into an analyzable solution form. Digestion efficiency refers to the rate and extent to which a sample is completely decomposed under a given condition, and recovery refers to the percentage of target analyte retained during digestion. The orthogonal design optimization method is used for finding out the optimal combination among digestion temperature, time, type of digestion agent and dosage. By orthogonal design, these variables can be systematically varied and their effect on the solution efficiency and recovery evaluated.
And obtaining an analysis result of the microwave digestion parameters through a data analysis method, and obtaining a microwave digestion parameter corresponding to the maximum value of the analysis result to be recorded as an optimal microwave digestion parameter, wherein the common data analysis method comprises variance analysis, regression analysis and the like. In the embodiment, data obtained by orthogonal design experiments are processed through analysis of variance, and which variable combinations can maximize digestion efficiency and recovery rate are found out.
Carrying out digestion treatment according to the optimal microwave digestion parameters, and acquiring temperature parameters and pressure parameters in the digestion treatment process by a real-time monitoring method; and adjusting the optimal microwave digestion parameters through an optimization algorithm according to the temperature parameters and the pressure parameters. When the digestion treatment is carried out under the optimal microwave digestion parameters, the temperature parameters and the pressure parameters in the digestion process are monitored in real time through the sensor, and the temperature parameters and the pressure parameters directly influence the digestion efficiency and the safety. The optimization algorithm aims to ensure that the digestion process is carried out under the optimal condition, and meanwhile unsafe factors such as overheating, overvoltage and the like are avoided.
Further, the electrochemical detection method uses an electrochemical sensor comprising a mercury-specific sensitive material, and the method comprises:
the sensitive material is an aptamer rich in thymine, and the electrochemical sensor is obtained by connecting the aptamer rich in thymine on the surface of the nano-porous gold through a self-assembly method. The electrochemical sensor uses nano-porous gold (NPG) as a carrier material and on this basis self-assembles thymine-rich DNA aptamer (Ploy-T) via Au-S bonds. The electrochemical sensor Ploy-T/NPG/AuE exhibits good sensitivity and selectivity in detecting mercury due to the particularly high affinity of thymine-rich aptamers for mercury ions.
Finally, it should be noted that although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the technical solutions described in the foregoing embodiments, or equivalents may be substituted for some of the technical features thereof, and any modifications, equivalents, improvements or changes may be made without departing from the spirit and principle of the present invention.
Claims (9)
1. A method for detecting mercury content in solid waste, the method comprising:
obtaining a solid waste sample, crushing and screening according to a preset particle size to obtain a first sample, and randomly sampling and digesting the first sample to obtain a solution to be tested;
The method comprises the steps of obtaining effective response current of a solution to be detected through an electrochemical detection method, obtaining mercury content of the solution to be detected according to a standard relation curve of mercury content of the effective response current, and marking the mercury content as first mercury content;
Obtaining a predicted value of mercury content by a mercury content prediction model and marking the predicted value as second mercury content;
and obtaining a third mercury content by numerical analysis of the first mercury content and the second mercury content, and outputting the third mercury content in a text or graphic form.
2. The method for detecting the mercury content in the solid waste according to claim 1, wherein the method for obtaining the effective response current of the solution to be detected by an electrochemical detection method, and obtaining the mercury content of the solution to be detected according to a standard relation curve of the mercury content and recording the mercury content as the first mercury content comprises the following steps:
Obtaining a group of response currents through an electrochemical detection method, analyzing the group of response currents through normal distribution, obtaining response currents in a preset confidence interval, marking the response currents as reliable response currents, and calculating the reliable response currents through average values to obtain effective response currents;
Standard solution with known mercury content is obtained, standard response current is obtained through an electrochemical detection method, and a standard relation curve is obtained through least square fitting of the relation between the standard response current and the mercury content.
3. The method for detecting the mercury content in the solid waste according to claim 2, wherein the method for obtaining a set of response currents from the set of detection sample solutions through an electrochemical detection method comprises:
the set of test sample solutions is noted as The response current corresponding to the group of detection sample solutions is recorded asObtaining a detection sample solutionThe detection sample solutionObtaining a response current by applying a preset voltageThe preset voltage is the detection voltage of an electrochemical detection method;
subjecting the test sample solution to According to a preset voltage and a preset detection time interval, measuring to obtain M groups of corrected response currents, obtaining the deviation degree of the M groups of corrected response currents by adopting deviation difference analysis, and obtaining the response current by adopting a mean value algorithm from the response currents with the deviation degree smaller than a preset deviation threshold value。
4. The method for detecting mercury content in solid waste according to claim 3, wherein said M sets of corrected response currents are subjected to deviation analysis to obtain a deviation degree, and said response currents having the deviation degree smaller than a preset deviation threshold are subjected to a mean algorithm to obtain response currentsThe method of (1) comprises:
obtaining standard response currents of standard solutions at different temperatures when different detection voltages are applied, and fitting the standard response currents to obtain temperature correction curves of the different detection voltages;
the temperature of the detected sample solution is recorded as the target temperature when the measurement is not carried out, a temperature correction curve corresponding to the preset voltage is obtained, and correction coefficients of different temperatures and the target temperature are calculated according to the temperature correction curve;
Obtaining a test sample solution The method comprises the steps of measuring the actual measured temperature of response current, obtaining a corresponding correction coefficient according to the actual measured temperature, and correcting the response current through the correction coefficient to obtain corrected response current;
Subjecting the test sample solution toThe measured M sets of corrected response currents are recorded asObtaining a reference response current through a mean value calculation methodThe reference response currentObtaining the deviation degree of the M groups of correction response currents through deviation analysisThe degree of deviationThe calculation formula of (2) is as follows:
;
Will correct the response current And reference response currentIs smaller than the deviation degreeIs a correction response current of (a)Reserve and record as qualified response currentAnd passing the qualified response currentObtaining response current through mean value calculation method。
5. A method for detecting mercury content in solid waste as claimed in claim 3, further comprising:
Obtaining a preset voltage test sample solution, determining a preset voltage according to a scanning algorithm, obtaining an adjustment voltage according to an initial voltage, an adjustment time interval and an adjustment voltage difference value preset by the scanning algorithm, obtaining a response current corresponding to the adjustment voltage, drawing a voltage current curve, obtaining an adjustment voltage corresponding to a peak response current of the voltage current curve, and recording the adjustment voltage as the preset voltage.
6. The method for detecting the mercury content in the solid waste according to claim 1, wherein the step of obtaining the characteristic signal related to the mercury content of the solution to be detected, and the step of obtaining the predicted value of the mercury content from the characteristic signal through a mercury content prediction model and recording the predicted value as the second mercury content comprises the following steps:
the characteristic signals comprise effective response current of the solution to be detected, corresponding preset voltage and types and proportions of solid wastes for preparing the solution to be detected;
The method comprises the steps of obtaining the type, the proportion, the effective response current and the corresponding preset voltage of the solid waste detected by the historical mercury content, wherein the mercury content prediction model is used for establishing the mapping relation between the type, the proportion, the effective response current and the corresponding preset voltage of the solid waste and the mercury content through a deep learning algorithm.
7. The method for detecting the mercury content in the solid waste according to claim 1, wherein the method for obtaining the third mercury content by analyzing the first mercury content and the second mercury content through numerical analysis comprises the following steps:
At the first mercury content And a second mercury content ofWhen the absolute percentage difference of the first mercury content and the second mercury content is smaller than a preset difference threshold value, obtaining a third mercury content through a mean algorithmUpdating and training a mercury content prediction model;
At the first mercury content And a second mercury content ofWhen the absolute percentage difference of the mercury is larger than a preset difference threshold value, the mercury content is calculatedRe-detecting;
The mean value algorithm adopts a linear weighting algorithm to obtain the third mercury content First mercury contentAnd a second mercury content ofThe weight coefficients of (2) are respectively preset、And (2) andThird mercury contentThe method comprises the following steps:。
8. The method for detecting mercury content in solid waste according to claim 1, wherein the method for obtaining the solution to be detected by randomly sampling and digestion treatment of the first sample comprises the following steps:
the microwave digestion process adopts a microwave digestion method, and microwave digestion parameters are obtained through an orthogonal design optimization method according to a preset microwave digestion target, wherein the preset microwave digestion target comprises digestion efficiency and recovery rate, and the microwave digestion parameters comprise digestion temperature, digestion time, digestion agent types and consumption;
Obtaining an analysis result of the microwave digestion parameters through a data analysis method, and obtaining a microwave digestion parameter corresponding to the maximum value of the analysis result to be recorded as an optimal microwave digestion parameter;
carrying out digestion treatment according to the optimal microwave digestion parameters, and acquiring temperature parameters and pressure parameters in the digestion treatment process by a real-time monitoring method; and adjusting the optimal microwave digestion parameters through an optimization algorithm according to the temperature parameters and the pressure parameters.
9. A method for detecting mercury content in solid waste as claimed in claim 1, wherein the electrochemical sensor used in the electrochemical detection method comprises a method for containing mercury-specific sensitive material comprising:
The sensitive material is an aptamer rich in thymine, and the electrochemical sensor is obtained by connecting the aptamer rich in thymine on the surface of the nano-porous gold through a self-assembly method.
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