Method for stabilizing Mn < 2 + > and NH4 < + >-N in manganese slag by using humic acid

Abstract

The invention relates to the technical field of chemical substance treatment, in particular to a method for stabilizing Mn < 2 + > and NH4 < + >-N in manganese slag by using humic acid, which comprises the following steps: determining the content of Mn < 2 + > and NH4 < + >-N in electrolytic manganese slag by using an inductively coupled plasma spectrometer, combining with the mineral phase structure of the manganese slag, analyzing the mineral composition, and determining the putting amount of humic acid. And generating manganese slag mineral phase composition data. According to the method, the multi-target genetic algorithm is adopted, so that the system can optimize selective complexing conditions of humic acid under multiple targets, the complexing reaction path of Mn < 2 + > and NH4 < + >-N is ensured to be stable, unnecessary chemical side reactions are avoided, the decision tree algorithm is used for rapidly judging the optimal reaction path by screening the reaction conditions, and the optimal reaction path can be accurately determined. Preferential complexing of the humic acid and harmful ingredients in the manganese slag is ensured, meanwhile, the overall treatment efficiency is improved, the use of the humic acid is accurately controlled, and the purposes of improving the treatment effect and reducing the use amount of the humic acid are achieved.

Description

Technical Field

[0001] The invention relates to the technical field of chemical substance treatment, and in particular to a method for stabilizing Mn2+ and NH4+-N in manganese slag by utilizing humic acid. Background Art

[0002] The purpose of the field of chemical substance treatment technology is to reduce the emission of environmental pollutants or realize waste resource treatment. Using chemical substances to stabilize harmful components in waste or make them less likely to migrate and release is a common treatment method.

[0003] The main goal of the method of using humic acid to stabilize Mn2+ and NH4+-N in manganese slag is to reduce the migration and release of soluble Mn2+ and NH4+-N in manganese slag, reduce the migration and fixation of metal ions in water through the adsorption, chelation and precipitation of humic acid, and at the same time stabilize the divalent manganese and ammonium nitrogen in the manganese slag and reduce the solubility of manganese ions and ammonium nitrogen.

[0004] Traditional chemical treatment methods lack the support of intelligent algorithms, which makes it difficult to accurately control the reaction conditions, affecting the overall treatment effect. It is difficult to take into account the variables of the reaction system at the same time. Unstable chemical reactions are prone to occur during the treatment process, resulting in the migration and release of Mn2+ and NH4+-N. In addition, due to insufficient monitoring of the reaction process and unclear reaction paths, traditional methods are prone to generate a variety of by-products, which increases the difficulty and cost of subsequent treatment. Summary of the invention

[0005] The purpose of the present invention is to solve the shortcomings of the prior art and to propose a method for stabilizing Mn2+ and NH4+-N in manganese slag by using humic acid.

[0006] In order to achieve the above object, the present invention adopts the following technical scheme: a method for stabilizing Mn2+ and NH4+-N in manganese slag by using humic acid, comprising the following steps:

[0007] Step 1: Analyze the composition of electrolytic manganese slag based on inductively coupled plasma spectrometer, determine the ion concentration of the sample, measure the specific content of Mn2+ and NH4+-N one by one, and analyze its mineral composition by comparing data in combination with the mineral phase structure information of manganese slag, determine the amount of humic acid added, and generate the mineral phase composition data of manganese slag;

[0008] Step 2: Based on the mineral phase composition data of the manganese slag, the reaction between humic acid and manganese slag is monitored in real time by Fourier transform infrared spectroscopy technology, the functional group analysis of the intermediate substances and the final product in the reaction is performed, the specific binding points and binding modes of Mn2+ and NH4+-N in the reaction process are identified, the complex structure is determined, and the reaction path data of the humic acid complex is obtained;

[0009] Step 3: Based on the humic acid complex reaction path data, the rate of the reaction between manganese slag and humic acid at different temperatures is measured to determine the time of reactant consumption and the rate of product formation, and the concentration ratio of humic acid is adjusted by controlling the reaction temperature and time to generate humic acid selective reaction rate data;

[0010] Step 4: Based on the humic acid selective reaction rate data, a multi-objective genetic algorithm is used to gradually adjust the humic acid dosage and the pH value in the reaction medium by real-time monitoring of the pH value in the reaction system, and selectively adjust the complexation conditions of Mn2+ and NH4+-N to ensure a stable reaction path and generate pH control reaction condition data;

[0011] Step 5: Based on the pH control reaction condition data, a decision tree algorithm is used to screen the parameters of reaction temperature, time and humic acid addition, determine the priority complexation path of Mn2+ and NH4+-N in manganese slag, determine the optimal reaction path, set the final parameters, optimize the humic acid complexation conditions, and obtain manganese slag complex product data;

[0012] Step 6: Based on the manganese slag complex product data, the residual Mn2+ and NH4+-N concentrations in the manganese slag after humic acid treatment are detected, the treatment efficiency is measured and analyzed, the actual treatment effect of the humic acid complex reaction is determined, and a humic acid stable complex result is generated.

[0013] As a further scheme of the present invention, the humic acid complex reaction path data includes functional group changes, reaction intermediate structures, and final complex structures; the humic acid selective reaction rate data includes temperature adjustment range, reaction rate constant, and reaction time of humic acid and manganese slag; the manganese slag complex product data includes complex molecular structure, optimal reaction temperature, and reaction time; the humic acid stable complexation results include Mn2+ residual amount, NH4+-N stability rate, and chemical stability of the complex.

[0014] As a further solution of the present invention, the specific steps of generating the manganese slag mineral phase composition data are:

[0015] Based on the inductively coupled plasma spectrometer, the ion concentration of the electrolytic manganese slag sample was determined, and the specific content of Mn2+ and NH4+-N was measured one by one. The concentration was recorded by separating different ions in the sample. After completion, the content of each ion was comprehensively calculated to generate the manganese slag ion concentration data;

[0016] Based on the manganese slag ion concentration data, the manganese slag mineral phase structure information is analyzed, and through sample processing and mineral composition analysis, different mineral types are compared one by one to determine the proportion of each mineral phase in the sample, and generate manganese slag mineral composition data;

[0017] Based on the manganese slag mineral composition data and the humic acid dosage requirements, the reactivity of each mineral with humic acid is calculated, the dosage is adjusted, the dosage is obtained based on the comprehensive reaction ratio of each mineral, and the manganese slag mineral phase composition data is generated.

[0018] As a further solution of the present invention, the specific steps of generating the humic acid complex reaction path data are:

[0019] Based on the manganese slag mineral phase composition data, Fourier transform infrared spectroscopy monitoring is performed, the manganese slag sample is processed, infrared spectroscopy data during the reaction of humic acid and manganese slag is obtained, intermediate substances formed by the reaction are analyzed, and humic acid reaction intermediate substance data is generated;

[0020] Based on the humic acid reaction intermediate substance data, the functional group changes of the intermediate substance are analyzed, and the binding sites of Mn2+ and NH4+-N are identified in combination with the spectral data, and their binding modes are recorded item by item to generate Mn2+ and NH4+-N binding mode data;

[0021] Based on the Mn2+ and NH4+-N binding mode data, the complex formation path of humic acid with Mn2+ and NH4+-N is analyzed, the stability and structural changes of the complex in each reaction step are recorded, and the humic acid complex reaction path data is generated.

[0022] As a further embodiment of the present invention, the specific steps of generating the humic acid selective reaction rate data are as follows:

[0023] Based on the reaction path data of humic acid complex, the reaction experiment of manganese slag and humic acid at different temperatures was carried out, and the reaction rate was measured by gradually increasing the temperature. By recording the consumption of the reactants after each temperature change, the consumption time data of the reactants was obtained, and the reaction rate data of manganese slag was generated.

[0024] Based on the reaction rate data of manganese slag, by setting different time intervals and adjusting the temperature parameters in the experiment, the humic acid concentration under each temperature condition was measured respectively, the formation time of the reaction products was recorded one by one, and the temperature and concentration relationship data were generated;

[0025] Based on the temperature and concentration relationship data, by comparing the changes in reaction rate at different temperatures, the humic acid concentration ratio is adjusted, and the temperature in the reaction system is precisely adjusted. The optimal reaction time and ratio parameters are recorded to generate humic acid selective reaction rate data.

[0026] As a further solution of the present invention, the specific steps of generating the pH control reaction condition data are:

[0027] Based on the humic acid selective reaction rate data, a multi-objective genetic algorithm is used to monitor the pH value of the reaction system, and a real-time recording device is used to gradually adjust the amount of humic acid added, control the pH change in the reaction system, record the pH change at each stage, and generate data on the relationship between the amount of humic acid added and the pH value;

[0028] Based on the data on the relationship between the dosage and the pH value, combined with the concentrations of Mn2+ and NH4+-N measured in the reaction, the progress of the complexation reaction is monitored by gradually adjusting the pH value in the reaction medium, the effect of the pH value on the formation of the complex is recorded, and the data on the effect of the pH value on the reaction is generated;

[0029] Based on the data on the effect of pH on the reaction, the stable complexation process of Mn2+ and NH4+-N under the reaction conditions was analyzed, the pH and the amount of humic acid added in the reaction were gradually adjusted, the pH value in the system was controlled and the optimal adjustment parameters were recorded to generate pH control reaction condition data.

[0030] As a further solution of the present invention, the multi-objective genetic algorithm is according to the formula:

[0031]

[0032] Where: f(x) is the fitness function, w i is the weight coefficient of the priority of the reaction stage, R i (pH) is the pH value monitored at stage i, is the target pH value of the i-th stage, n is the number of stages of humic acid addition, λ is the temperature deviation correction coefficient, T i (t) is the reaction temperature monitored at stage i, is the target temperature of the i-th stage, μ is the humic acid concentration deviation correction coefficient, C i (CA) is the humic acid concentration in stage i, is the target concentration in stage i.

[0033] As a further embodiment of the present invention, the specific steps of generating the manganese slag complex product data are:

[0034] Based on the pH control reaction condition data, the decision tree algorithm was used to screen the reaction temperature and time. The temperature was gradually increased to record the reaction rate under each temperature condition. The temperature and time screening data were generated by measuring the changes in the concentrations of Mn2+ and NH4+-N in the sample.

[0035] Based on the temperature-time screening data, the amount of humic acid added was gradually adjusted. The amount was gradually increased, and the complexation paths of Mn2+ and NH4+-N under different concentration conditions were recorded. The priority complexation order was determined, and the priority complexation path data was generated.

[0036] Based on the preferential complexation path data and combined with the previous screening results of temperature, time and humic acid concentration, the optimal reaction conditions were determined, the set reaction parameters were verified through experiments, the final complex formation was recorded, and the manganese slag complex product data was generated.

[0037] As a further solution of the present invention, the decision tree algorithm is according to the formula:

[0038]

[0039] Where: R is the reaction rate, k is the reaction rate constant, C(Mn 2+ ) is the concentration of Mn2+ in the sample, is the NH4+-N concentration in the sample, t is the reaction time, α is the influence coefficient of NH4+-N on the reaction rate, ΔT is the increment of the reaction temperature increase, and β is the correction coefficient of temperature change on the reaction rate.

[0040] As a further embodiment of the present invention, the specific steps for generating the humic acid stable complexation result are:

[0041] Based on the product data of manganese slag complex, the residual Mn2+ concentration in the manganese slag sample after humic acid treatment was detected. The step-by-step sample analysis method was used to measure the samples one by one after treatment, record the Mn2+ residue, and generate the Mn2+ residue detection data;

[0042] Based on the Mn2+ residual detection data, the NH4+-N residual concentration in the sample is measured. The same sample processing method is used to detect the concentration change of NH4+-N in different samples one by one, and the NH4+-N residual situation of each sample is recorded to generate NH4+-N residual detection data;

[0043] Based on the NH4+-N residual detection data and combined with the Mn2+ detection data, the residual amounts of the two ions in the manganese slag after humic acid treatment were analyzed, and a comprehensive data analysis was performed to obtain the final treatment efficiency and generate the humic acid stable complexation result.

[0044] Compared with the prior art, the advantages and positive effects of the present invention are:

[0045] 1. In the present invention, by using a multi-objective genetic algorithm, the system can optimize the selective complexing conditions of humic acid under multiple objectives, ensure the stability of the complexing reaction path of Mn2+ and NH4+-N, and avoid unnecessary chemical side reactions;

[0046] 2. The decision tree algorithm quickly determines the optimal reaction path by screening the reaction conditions, ensuring the priority complexation of humic acid with harmful components in manganese slag, while improving the overall treatment efficiency and accurately controlling the use of humic acid, thereby improving the treatment effect and reducing the amount of humic acid used. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] Figure 1 It is a schematic diagram of the main steps of the present invention. DETAILED DESCRIPTION

[0048] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0049] Embodiment 1

[0050] See also Figure 1 The present invention provides a technical solution: a method for stabilizing Mn2+ and NH4+-N in manganese slag by using humic acid, comprising the following steps:

[0051] Step 1: Analyze the composition of electrolytic manganese slag based on inductively coupled plasma spectrometer, determine the ion concentration of the sample, measure the specific content of Mn2+ and NH4+-N one by one, and analyze its mineral composition by comparing data in combination with the mineral phase structure information of manganese slag, determine the amount of humic acid added, and generate the mineral phase composition data of manganese slag;

[0052] Step 2: Based on the mineral phase composition data of manganese slag, the reaction between humic acid and manganese slag is monitored in real time by Fourier transform infrared spectroscopy technology, the functional groups of the intermediate substances and final products in the reaction are analyzed, the specific binding points and binding modes of Mn2+ and NH4+-N in the reaction process are identified, the complex structure is determined, and the reaction path data of the humic acid complex is obtained;

[0053] Step 3: Based on the reaction path data of humic acid complex, the rate of reaction between manganese slag and humic acid at different temperatures is measured to determine the time of reactant consumption and the rate of product formation. By controlling the reaction temperature and time, the concentration ratio of humic acid is adjusted to generate humic acid selective reaction rate data;

[0054] Step 4: Based on the selective reaction rate data of humic acid, a multi-objective genetic algorithm is used to monitor the pH value in the reaction system in real time, gradually adjust the amount of humic acid added and the pH value in the reaction medium, adjust the selective complexation conditions of Mn2+ and NH4+-N, ensure a stable reaction path, and generate pH control reaction condition data;

[0055] Step 5: Based on the pH control reaction condition data, a decision tree algorithm is used to screen the parameters of reaction temperature, time and humic acid addition, determine the priority complexation path of Mn2+ and NH4+-N in manganese slag, determine the optimal reaction path, set the final parameters, optimize the humic acid complexation conditions, and obtain the manganese slag complex product data;

[0056] Step 6: Based on the manganese slag complex product data, the residual Mn2+ and NH4+-N concentrations in the manganese slag after humic acid treatment are detected, the treatment efficiency is measured and analyzed, the actual treatment effect of the humic acid complex reaction is determined, and the humic acid stable complex result is generated.

[0057] The reaction path data of humic acid complex include functional group changes, reaction intermediate structure, and final complex structure. The selective reaction rate data of humic acid include temperature adjustment range, reaction rate constant, and reaction time of humic acid and manganese slag. The product data of manganese slag complex include complex molecular structure, optimal reaction temperature, and reaction time. The stable complexation results of humic acid include Mn2+ residual amount, NH4+-N stability rate, and chemical stability of the complex.

[0058] The specific steps to generate the mineral phase composition data of manganese slag are:

[0059] Based on the inductively coupled plasma spectrometer, the ion concentration of the electrolytic manganese slag sample was determined, and the specific content of Mn2+ and NH4+-N was measured one by one. The concentration was recorded by separating different ions in the sample. After completion, the content of each ion was comprehensively calculated to generate the manganese slag ion concentration data;

[0060] Based on the manganese slag ion concentration data, the mineral phase structure information of the manganese slag is analyzed. Through sample processing and mineral composition analysis, different mineral types are compared one by one to determine the proportion of each mineral phase in the sample and generate the manganese slag mineral composition data;

[0061] Based on the mineral composition data of manganese slag and the requirements for humic acid addition, the reactivity of each mineral with humic acid is calculated, the addition amount is adjusted, and the addition amount is obtained by comprehensively considering the reaction ratio of each mineral to generate the mineral phase composition data of manganese slag;

[0062] The ion concentration of the electrolytic manganese slag sample was determined based on an inductively coupled plasma spectrometer. The ICP-OES method parameters included a light source power of 1400W, an airflow rate of 15L / min, and a sample flow rate of 1mL / min. Mn2+ and NH4+-N in the sample were separated. The airflow rate and sample injection speed were adjusted to ensure that the ions were fully excited and detected. The peak intensities of different ions in the spectrum were recorded. The standard curve method was used to prepare a calibration curve for each element with a concentration range of 0-100mg / L. Concentration conversion and concentration calculation were performed to generate manganese slag ion concentration data.

[0063] Based on the manganese slag ion concentration data, the X-ray diffraction analysis method parameters include diffraction angle 2θ range of 5-90°, step size 0.02° / s, tube voltage 40kV, current 30mA, to analyze the manganese slag mineral phase structure. The sample is ground and the peak matching database is PDF-4 mineral database. The different mineral types are compared one by one, and the diffraction peak intensity of each mineral phase is recorded. By comparing the peak intensity with the peak value of the standard sample, the proportion of each mineral phase in the sample is determined to generate the manganese slag mineral composition data;

[0064] Based on the mineral composition data of manganese slag, a reactive calculation model, specifically the Langmuir isotherm adsorption model, was adopted. The model parameters included the adsorption constant K and the adsorption amount qmax. The dosage was calculated in combination with the reactivity of humic acid. The adsorption capacity and reaction equilibrium constant of each mineral were input respectively. The dosage of humic acid was adjusted according to the reactivity of each mineral. The iterative method was used to optimize the dosage ratio of humic acid to generate the mineral phase composition data of manganese slag.

[0065] The specific steps for generating the humic acid complex reaction pathway data are:

[0066] Based on the mineral phase composition data of manganese slag, Fourier transform infrared spectroscopy monitoring is carried out, manganese slag samples are processed, infrared spectral data of the reaction between humic acid and manganese slag are obtained, intermediate substances formed by the reaction are analyzed, and data of intermediate substances in humic acid reaction are generated;

[0067] Based on the data of intermediate substances in humic acid reaction, the functional group changes of intermediate substances were analyzed, and the binding sites of Mn2+ and NH4+-N were identified by combining spectral data. The binding modes were recorded item by item to generate the binding mode data of Mn2+ and NH4+-N.

[0068] Based on the binding mode data of Mn2+ and NH4+-N, the complex formation pathways of humic acid with Mn2+ and NH4+-N were analyzed, the stability and structural changes of the complexes in each reaction step were recorded, and the reaction pathway data of humic acid complexes were generated;

[0069] Based on the mineral phase composition data of manganese slag, the manganese slag samples were processed using Fourier transform infrared spectroscopy technology. Through the ATR mode, the parameters included spectral resolution of 4cm-1, scanning times of 32 times, and wavenumber range of 4000-400cm-1. The infrared spectrum data at different time points in the reaction process of humic acid and manganese slag were gradually obtained. The infrared absorption peaks of the intermediate substances formed by humic acid and manganese slag were identified and recorded using the absorption peak position and intensity analysis method. The frequency conversion was performed to separate the infrared characteristic peaks corresponding to different functional groups, and the data of the intermediate substances of the humic acid reaction were generated.

[0070] Based on the data of intermediate substances in humic acid reaction, the infrared spectrum data of the intermediate substances were analyzed by the functional group analysis method. The frequency matching method was used, and the parameters were the infrared absorption peak positions of common functional groups, hydroxyl 3200-3600cm-1, carbonyl 1650-1750cm-1. The functional group absorption peak positions of the intermediate substances were compared one by one, and the binding sites of Mn2+ and NH4+-N were identified. The binding modes were gradually recorded, and the binding energy calculation method was used to record the energy changes in the binding process, generating the binding mode data of Mn2+ and NH4+-N.

[0071] Based on the Mn2+ and NH4+-N binding mode data, the complex pathway analysis method was used to analyze each step in the complex reaction of humic acid with Mn2+ and NH4+-N one by one. The molecular orbital calculation method was used with parameters including HOMO-LUMO energy gap and reaction orbital number 3 to record the stability and structural changes of each reaction step in the formation of humic acid complexes, and generate the humic acid complex reaction pathway data.

[0072] The specific steps to generate humic acid selective reaction rate data are:

[0073] Based on the reaction path data of humic acid complex, the reaction experiment of manganese slag and humic acid at different temperatures was carried out, and the reaction rate was measured by gradually increasing the temperature. By recording the consumption of the reactants after each temperature change, the consumption time data of the reactants was obtained, and the reaction rate data of manganese slag was generated.

[0074] Based on the reaction rate data of manganese slag, by setting different time intervals and adjusting the temperature parameters in the experiment, the humic acid concentration under each temperature condition was measured respectively, the formation time of the reaction products was recorded one by one, and the temperature and concentration relationship data were generated;

[0075] Based on the temperature and concentration relationship data, by comparing the changes in reaction rates at different temperatures, the humic acid concentration ratio is adjusted, and the temperature in the reaction system is precisely adjusted, the optimal reaction time and ratio parameters are recorded, and the humic acid selective reaction rate data is generated;

[0076] Based on the reaction path data of humic acid complex, the reaction experiment of manganese slag and humic acid at different temperatures was carried out. The temperature control method was used to gradually increase the temperature to measure the reaction rate. The parameters included a temperature increment of 5°C each time and a maximum temperature set at 80°C. After each temperature change, the consumption of the reactants Mn2+ and NH4+-N was recorded. The consumption rate of the reactants was calculated using the differential reaction method. The concentration of the reactants at each reaction time node was recorded, and the consumption time of the reactants at each temperature was calculated to generate the manganese slag reaction rate data.

[0077] Based on the reaction rate data of manganese slag, different time intervals were set and the multi-point temperature control method was used. The parameter was to adjust the temperature every 10 minutes, ranging from 20°C to 80°C. The humic acid concentration was measured under each temperature condition. The concentration was measured by titration. The titrant was 0.1 mol / L NaOH solution. The formation time of the reaction product was recorded step by step. The relationship between the time interval and the concentration was calculated by the time series analysis method to generate the temperature and concentration relationship data.

[0078] Based on the temperature and concentration relationship data, by comparing the changes in reaction rate at different temperatures, a concentration control model is adopted. The parameters are the linear fitting equation of the temperature and concentration relationship. The humic acid concentration ratio is adjusted, and the temperature in the reaction system is accurately adjusted according to the fitting equation. The optimal reaction time and humic acid ratio parameters at each temperature are recorded to generate humic acid selective reaction rate data.

[0079] The specific steps for generating pH control reaction condition data are:

[0080] Based on the selective reaction rate data of humic acid, a multi-objective genetic algorithm was used to monitor the pH value of the reaction system. The amount of humic acid added was gradually adjusted using real-time recording equipment to control the pH changes in the reaction system, record the pH changes at each stage, and generate data on the relationship between the amount of humic acid added and the pH value.

[0081] Based on the data on the relationship between the dosage and pH value, combined with the Mn2+ and NH4+-N concentrations measured during the reaction, the pH value in the reaction medium was gradually adjusted to monitor the progress of the complexation reaction, record the effect of pH value on complex formation, and generate data on the effect of pH value on the reaction;

[0082] Based on the data on the effect of pH on the reaction, the stable complexation process of Mn2+ and NH4+-N under the reaction conditions was analyzed, the pH and the amount of humic acid added in the reaction were gradually adjusted, the pH value in the system was controlled and the optimal adjustment parameters were recorded, and the pH control reaction condition data was generated;

[0083] Based on the selective reaction rate data of humic acid, a multi-objective genetic algorithm was used to monitor the pH value of the reaction system. The parameters included a population size of 50, a crossover rate of 0.8, and a mutation rate of 0.05. A pH sensor was used to record the pH value in the reaction system in real time. The amount of humic acid added was gradually adjusted. The step-by-step method was used, and the increase in the amount of humic acid added each time was 0.1 g / L. The pH value changes in the reaction system were controlled, the pH value changes at each stage were recorded, and the pH data were collected and processed to generate the relationship data between the amount of humic acid added and the pH value.

[0084] Based on the data on the relationship between the dosage and the pH value, combined with the concentrations of Mn2+ and NH4+-N measured by the ion-selective electrode method during the reaction, the pH in the reaction medium was gradually adjusted. A feedback control system was used, with the pH adjustment amplitude of 0.2 units each time to monitor the progress of the complexation reaction, and the effect of the pH value on the formation of the humic acid complex was recorded in real time. The pH fluctuation during the reaction was recorded using a dynamic monitoring method to generate data on the effect of the pH value on the reaction.

[0085] Based on the data on the effect of pH on the reaction, the complex reaction kinetic model was used to analyze the stable complexation process of Mn2+ and NH4+-N under the reaction conditions. The pH value and the amount of humic acid added in the reaction were gradually adjusted. The gradient adjustment method was used, and the pH adjustment amplitude was 0.1 unit each time. The pH values ​​at different stages were recorded, and the optimal adjustment parameters were used to control the pH value in the reaction system to generate pH control reaction condition data.

[0086] Multi-objective genetic algorithm, according to the formula:

[0087]

[0088] Where: f(x) is the fitness function, w i is the weight coefficient of the priority of the reaction stage, R i (pH) is the pH value monitored at stage i, is the target pH value of the i-th stage, n is the number of stages of humic acid addition, λ is the temperature deviation correction coefficient, T i (t) is the reaction temperature monitored at stage i, is the target temperature of the i-th stage, μ is the humic acid concentration deviation correction coefficient, C i (CA) is the humic acid concentration in stage i, is the target concentration in stage i;

[0089] Implementation process: According to the humic acid selective reaction rate data and pH monitoring results, record the pH changes at each stage and substitute the data into the R i 9pH) part, target pH value According to the set requirements, temperature is introduced as a new constraint condition, and the reaction temperature data T of each stage is monitored in real time. i (t), and the target temperature By comparison, the correction coefficient λ is used to control the effect of temperature on the entire reaction, and the weight coefficient w i The correction coefficient λ needs to be adjusted in combination with the experimental data. The specific method is to determine the degree of influence on the final pH value change based on the results of the previous rounds of experiments, calculate the optimal coefficient value, take the humic acid concentration as the third optimization target, and monitor the humic acid concentration C at each stage. i(CA) and target concentration For comparison, the concentration deviation correction coefficient μ is used for control. μ is obtained through experimental data analysis. By calculating the result of the formula f(x), the reaction optimization effect at the current stage can be judged and the amount of humic acid added can be adjusted in real time.

[0090] The specific steps for generating the manganese slag complex product data are:

[0091] Based on the pH control reaction condition data, the decision tree algorithm was used to screen the reaction temperature and time. The temperature was gradually increased to record the reaction rate under each temperature condition. The temperature and time screening data were generated by measuring the changes in the concentrations of Mn2+ and NH4+-N in the sample.

[0092] Based on the temperature-time screening data, the amount of humic acid added was gradually adjusted. The amount was gradually increased, and the complexation paths of Mn2+ and NH4+-N under different concentration conditions were recorded. The priority complexation order was determined, and the priority complexation path data was generated.

[0093] Based on the preferential complexation path data, combined with the previous screening results of temperature, time and humic acid concentration, the optimal reaction conditions were determined, the set reaction parameters were verified by experiments, the final complex formation was recorded, and the manganese slag complex product data was generated;

[0094] Based on the pH control reaction condition data, the decision tree algorithm was used to screen the reaction temperature and time. The parameters included the maximum tree depth of 10, the segmentation criterion was information gain, and the method of gradually increasing the temperature was set to increase by 5°C each time. The reaction rate under each temperature condition was recorded, and the linear regression method was used to measure the changes in the concentrations of Mn2+ and NH4+-N in the sample. The reaction rate corresponding to each temperature was calculated to generate temperature and time screening data.

[0095] Based on the temperature-time screening data, the amount of humic acid added was gradually adjusted, and the incremental control method was used. The amount was increased by 0.5 g / L each time. The complexation paths of Mn2+ and NH4+-N under different concentration conditions were recorded. The reaction path tracking algorithm was used to gradually identify the priority complexation order of Mn2+ and NH4+-N. By combining the intermediate state of complex formation, the time nodes of different complex formation were recorded to generate the priority complexation path data.

[0096] Based on the preferential complexation path data and combined with the previous screening results of temperature, time and humic acid concentration, the experimental verification method was used to set the optimal reaction conditions. The progress of the complexation reaction was monitored by a real-time monitoring system, the reaction temperature and time were gradually adjusted, and the formation of humic acid complexes was recorded to generate manganese slag complex product data.

[0097] Decision tree algorithm, according to the formula:

[0098]

[0099] Where: R is the reaction rate, k is the reaction rate constant, C(Mn 2+ ) is the concentration of Mn2+ in the sample, is the NH4+-N concentration in the sample, t is the reaction time, α is the influence coefficient of NH4+-N on the reaction rate, ΔT is the increment of the reaction temperature increase, and β is the correction coefficient of temperature change on the reaction rate;

[0100] Execution process: First, determine the reaction rate constant k by adjusting the temperature, then start measuring the concentration C (Mn 2+ ), and record changes over time through regular sampling, while monitoring the concentration Combined with the experiment, the influence coefficient α of ammonia nitrogen on the reaction rate is determined, and its value is usually between 0.1 and 0.3. Next, by gradually increasing the temperature, the reaction time t under each temperature condition is recorded, and the reaction temperature increment ΔT is calculated at the same time, incorporating the influence range of the temperature correction factor β. Finally, the parameters are combined to generate the reaction rate data under each temperature condition, completing the temperature and time screening process.

[0101] The specific steps to generate the stable complexation result of humic acid are:

[0102] Based on the product data of manganese slag complex, the residual Mn2+ concentration in the manganese slag sample after humic acid treatment was detected. The step-by-step sample analysis method was used to measure the samples one by one after treatment, record the Mn2+ residue, and generate the Mn2+ residue detection data;

[0103] Based on the Mn2+ residual detection data, the NH4+-N residual concentration in the sample is measured. The same sample processing method is used to detect the concentration change of NH4+-N in different samples one by one, and the NH4+-N residual situation of each sample is recorded to generate NH4+-N residual detection data;

[0104] Based on the NH4+-N residual detection data and combined with the Mn2+ detection data, the residual amounts of the two ions in the manganese slag after humic acid treatment were analyzed, and a comprehensive data analysis was performed to obtain the final treatment efficiency and generate the humic acid stable complexation results;

[0105] Based on the product data of manganese slag complex, the residual Mn2+ concentration in the manganese slag samples after humic acid treatment was detected. The manganese slag samples were pretreated by centrifugation and filtration using a step-by-step sample analysis method. The Mn2+ concentration in the samples was measured one by one using an inductively coupled plasma mass spectrometer. The parameters included a plasma power of 1500W and an injection rate of 1mL / min. The residual Mn2+ in each sample was recorded to generate Mn2+ residual detection data.

[0106] Based on the Mn2+ residual detection data, the NH4+-N residual concentration in the sample was determined. The same sample processing method as Mn2+ was used to determine the concentration change of NH4+-N by Kjeldahl nitrogen determination. The Kjeldahl nitrogen determination equipment parameters included a digestion temperature of 420°C and a distillation rate of 10mL / min. The NH4+-N concentrations of different samples were detected and recorded one by one to generate NH4+-N residual detection data.

[0107] Based on the NH4+-N residual detection data and combined with the Mn2+ detection data, the residual amounts of the two ions in the manganese slag after humic acid treatment were analyzed by multivariate linear regression analysis. The ion concentration and treatment time were input as regression parameters, and the changing trend of the residual amount was gradually fitted to generate the humic acid stable complexation result.

[0108] The above are only preferred embodiments of the present invention and are not intended to limit the present invention in other forms. Any technician familiar with the profession may use the technical contents disclosed above to change or modify them into equivalent embodiments with equivalent changes and apply them to other fields. However, any simple modification, equivalent change and modification made to the above embodiments based on the technical essence of the present invention without departing from the technical solution of the present invention still falls within the protection scope of the technical solution of the present invention.

Claims

1. A method for stabilizing Mn2+ and NH4+-N in manganese slag using humic acid, characterized in that: The following steps are involved: Step 1: Analyze the composition of electrolytic manganese slag based on inductively coupled plasma spectrometer, determine the ion concentration of the sample, measure the specific content of Mn2+ and NH4+-N one by one, and analyze its mineral composition by comparing data in combination with the mineral phase structure information of manganese slag, determine the amount of humic acid added, and generate the mineral phase composition data of manganese slag; Step 2: Based on the mineral phase composition data of the manganese slag, the reaction between humic acid and manganese slag is monitored in real time by Fourier transform infrared spectroscopy technology, the functional group analysis of the intermediate substances and the final product in the reaction is performed, the specific binding points and binding modes of Mn2+ and NH4+-N in the reaction process are identified, the complex structure is determined, and the reaction path data of the humic acid complex is obtained; Step 3: Based on the humic acid complex reaction path data, the rate of the reaction between manganese slag and humic acid at different temperatures is measured to determine the time of reactant consumption and the rate of product formation, and the concentration ratio of humic acid is adjusted by controlling the reaction temperature and time to generate humic acid selective reaction rate data; Step 4: Based on the humic acid selective reaction rate data, a multi-objective genetic algorithm is used to gradually adjust the humic acid dosage and the pH value in the reaction medium by real-time monitoring of the pH value in the reaction system, and selectively adjust the complexation conditions of Mn2+ and NH4+-N to ensure a stable reaction path and generate pH control reaction condition data; Step 5: Based on the pH control reaction condition data, a decision tree algorithm is used to screen the parameters of reaction temperature, time and humic acid addition, determine the priority complexation path of Mn2+ and NH4+-N in manganese slag, determine the optimal reaction path, set the final parameters, optimize the humic acid complexation conditions, and obtain manganese slag complex product data; Step 6: Based on the manganese slag complex product data, the residual Mn2+ and NH4+-N concentrations in the manganese slag after humic acid treatment are detected, the treatment efficiency is measured and analyzed, the actual treatment effect of the humic acid complex reaction is determined, and a humic acid stable complex result is generated.

2. The method for stabilizing Mn2+ and NH4+-N in manganese slag by using humic acid according to claim 1, characterized in that: The humic acid complex reaction path data include functional group changes, reaction intermediate structures, and final complex structures. The humic acid selective reaction rate data include temperature adjustment range, reaction rate constant, and reaction time of humic acid and manganese slag. The manganese slag complex product data include complex molecular structure, optimal reaction temperature, and reaction time. The humic acid stable complexation results include Mn2+ residual amount, NH4+-N stability rate, and chemical stability of the complex.

3. The method for stabilizing Mn2+ and NH4+-N in manganese slag by using humic acid according to claim 1, characterized in that: The specific steps of generating the manganese slag mineral phase composition data are: Based on the inductively coupled plasma spectrometer, the ion concentration of the electrolytic manganese slag sample was determined, and the specific content of Mn2+ and NH4+-N was measured one by one. The concentration was recorded by separating different ions in the sample. After completion, the content of each ion was comprehensively calculated to generate the manganese slag ion concentration data; Based on the manganese slag ion concentration data, the manganese slag mineral phase structure information is analyzed, and through sample processing and mineral composition analysis, different mineral types are compared one by one to determine the proportion of each mineral phase in the sample, and generate manganese slag mineral composition data; Based on the manganese slag mineral composition data and the humic acid dosage requirements, the reactivity of each mineral with humic acid is calculated, the dosage is adjusted, the dosage is obtained based on the comprehensive reaction ratio of each mineral, and the manganese slag mineral phase composition data is generated.

4. The method for stabilizing Mn2+ and NH4+-N in manganese slag by using humic acid according to claim 1, characterized in that: The specific steps of generating the humic acid complex reaction path data are: Based on the manganese slag mineral phase composition data, Fourier transform infrared spectroscopy monitoring is performed, the manganese slag sample is processed, infrared spectroscopy data during the reaction of humic acid and manganese slag is obtained, intermediate substances formed by the reaction are analyzed, and humic acid reaction intermediate substance data is generated; Based on the humic acid reaction intermediate substance data, the functional group changes of the intermediate substance are analyzed, and the binding sites of Mn2+ and NH4+-N are identified in combination with the spectral data, and their binding modes are recorded item by item to generate Mn2+ and NH4+-N binding mode data; Based on the Mn2+ and NH4+-N binding mode data, the complex formation path of humic acid with Mn2+ and NH4+-N is analyzed, the stability and structural changes of the complex in each reaction step are recorded, and the humic acid complex reaction path data is generated.

5. The method for stabilizing Mn2+ and NH4+-N in manganese slag by using humic acid according to claim 1, characterized in that: The specific steps for generating the humic acid selective reaction rate data are: Based on the reaction path data of humic acid complex, the reaction experiment of manganese slag and humic acid at different temperatures was carried out, and the reaction rate was measured by gradually increasing the temperature. By recording the consumption of the reactants after each temperature change, the consumption time data of the reactants was obtained, and the reaction rate data of manganese slag was generated. Based on the reaction rate data of manganese slag, by setting different time intervals and adjusting the temperature parameters in the experiment, the humic acid concentration under each temperature condition was measured respectively, the formation time of the reaction products was recorded one by one, and the temperature and concentration relationship data were generated; Based on the temperature and concentration relationship data, by comparing the changes in reaction rate at different temperatures, the humic acid concentration ratio is adjusted, and the temperature in the reaction system is precisely adjusted. The optimal reaction time and ratio parameters are recorded to generate humic acid selective reaction rate data.

6. The method for stabilizing Mn2+ and NH4+-N in manganese slag by using humic acid according to claim 1, characterized in that: The specific steps of generating the pH control reaction condition data are: Based on the humic acid selective reaction rate data, a multi-objective genetic algorithm is used to monitor the pH value of the reaction system, and a real-time recording device is used to gradually adjust the amount of humic acid added, control the pH change in the reaction system, record the pH change at each stage, and generate data on the relationship between the amount of humic acid added and the pH value; Based on the data on the relationship between the dosage and the pH value, combined with the concentrations of Mn2+ and NH4+-N measured in the reaction, the progress of the complexation reaction is monitored by gradually adjusting the pH value in the reaction medium, the effect of the pH value on the formation of the complex is recorded, and the data on the effect of the pH value on the reaction is generated; Based on the data on the effect of pH on the reaction, the stable complexation process of Mn2+ and NH4+-N under the reaction conditions was analyzed, the pH and the amount of humic acid added in the reaction were gradually adjusted, the pH value in the system was controlled and the optimal adjustment parameters were recorded to generate pH control reaction condition data.

7. The method for stabilizing Mn2+ and NH4+-N in manganese slag by using humic acid according to claim 1, characterized in that: The multi-objective genetic algorithm is based on the formula: Where: f ( x) is the fitness function, w i is the weight coefficient of the priority of the reaction stage, R i (pH) is the pH value monitored at stage i, is the target pH value of the i-th stage, n is the number of stages of humic acid addition, λ is the temperature deviation correction coefficient, T i ( t ) is the reaction temperature monitored at stage i, is the target temperature of the i-th stage, μ is the humic acid concentration deviation correction coefficient, C i( CA ) is the humic acid concentration in stage i, is the target concentration in stage i.

8. The method for stabilizing Mn2+ and NH4+-N in manganese slag by using humic acid according to claim 1, characterized in that: The specific steps of generating the manganese slag complex product data are: Based on the pH control reaction condition data, the decision tree algorithm was used to screen the reaction temperature and time. The temperature was gradually increased to record the reaction rate under each temperature condition. The temperature and time screening data were generated by measuring the changes in the concentrations of Mn2+ and NH4+-N in the sample. Based on the temperature-time screening data, the amount of humic acid added was gradually adjusted. The amount was gradually increased, and the complexation paths of Mn2+ and NH4+-N under different concentration conditions were recorded. The priority complexation order was determined, and the priority complexation path data was generated. Based on the preferential complexation path data and combined with the previous screening results of temperature, time and humic acid concentration, the optimal reaction conditions were determined, the set reaction parameters were verified through experiments, the final complex formation was recorded, and the manganese slag complex product data was generated.

9. The method for stabilizing Mn2+ and NH4+-N in manganese slag by using humic acid according to claim 1, characterized in that: The decision tree algorithm is based on the formula: Where: R is the reaction rate, k is the reaction rate constant, C ( Mn 2+ ) is the concentration of Mn2+ in the sample, is the NH4+-N concentration in the sample, t is the reaction time, α is the influence coefficient of NH4+-N on the reaction rate, ΔT is the increment of the reaction temperature increase, and β is the correction coefficient of temperature change on the reaction rate.

10. The method for stabilizing Mn2+ and NH4+-N in manganese slag by using humic acid according to claim 1, characterized in that: The specific steps of generating the humic acid stable complexation result are: Based on the product data of manganese slag complex, the residual Mn2+ concentration in the manganese slag sample after humic acid treatment was detected. The step-by-step sample analysis method was used to measure the samples one by one after treatment, record the Mn2+ residue, and generate the Mn2+ residue detection data; Based on the Mn2+ residual detection data, the NH4+-N residual concentration in the sample is measured. The same sample processing method is used to detect the concentration change of NH4+-N in different samples one by one, and the NH4+-N residual situation of each sample is recorded to generate NH4+-N residual detection data; Based on the NH4+-N residual detection data and combined with the Mn2+ detection data, the residual amounts of the two ions in the manganese slag after humic acid treatment were analyzed, and a comprehensive data analysis was performed to obtain the final treatment efficiency and generate the humic acid stable complexation result.

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