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CN-121978320-A - Online identification method and system for imidazolium resin adsorption kinetic parameters

CN121978320ACN 121978320 ACN121978320 ACN 121978320ACN-121978320-A

Abstract

The invention relates to the technical field of adsorption detection and discloses an on-line identification method and system for the adsorption kinetic parameters of imidazolium resin, wherein the method comprises the following steps of 1, synchronously collecting flow, inlet and outlet water concentration, conductivity, temperature and pH value, and obtaining apparent ionic strength from the conductivity; the method comprises the steps of (1) carrying out mass balance calculation based on flow, water inlet and outlet concentration and resin dry basis mass to obtain a resin average adsorption quantity real-time track, (3) constructing a counter ion coupling isothermal driving force and screening a quasi-balance section, (4) solving isothermal coupling parameters in a simultaneous quasi-balance relation mode, (5) calculating an integral mass transfer coefficient point by point, (6) solving an outer membrane mass transfer proportion coefficient and an in-hole mass transfer coefficient simultaneously under two-gear flow, and (7) constructing a core parameter set and outputting a consistency judgment result identifier. The invention realizes the on-line identification and consistency judgment of the adsorption thermodynamic parameter and the mass transfer kinetic parameter of the imidazolium resin.

Inventors

  • GU LONG
  • Su Xingkang
  • WANG GUAN

Assignees

  • 福建睿斯科医疗技术有限公司

Dates

Publication Date
20260505
Application Date
20260408

Claims (10)

  1. 1. The on-line identification method for the adsorption kinetic parameters of the imidazolium resin is characterized by comprising the following steps of: Step 1, synchronously collecting flow, inlet water concentration, outlet water concentration, conductivity, temperature and pH value, and obtaining apparent ionic strength from the conductivity according to a preset calibration relation; step 2, carrying out mass balance calculation according to the flow, the inflow water concentration, the outflow water concentration and the resin dry basis mass to obtain a real-time track of the resin average adsorption quantity; Step 3, constructing a counter ion coupling isothermal driving force based on the maximum adsorption capacity, the effluent concentration, the apparent ion intensity and the effective affinity coefficient of the resin, and screening a quasi-equilibrium section according to the change rate of the average adsorption capacity of the resin; Step 4, for the quasi-equilibrium sections corresponding to two different apparent ionic strengths, obtaining a parallel quasi-equilibrium relation between the average adsorption capacity of the resin and the water outlet concentration, and solving isothermal coupling parameters; step 5, substituting isothermal coupling parameters into the counter ion coupling isothermal driving force, and calculating an overall mass transfer coefficient point by point based on the linear driving force dynamic skeleton by the resin average adsorption quantity and the counter ion coupling isothermal driving force; Step 6, screening a counter ion state stable section, sequentially setting two-gear flow in the counter ion state stable section, acquiring a corresponding integral mass transfer coefficient, establishing a resistance series equation by combining a preset flow power law index, solving an outer membrane mass transfer proportional coefficient and an in-hole mass transfer coefficient, and acquiring an outer membrane mass transfer coefficient; And 7, forming a core parameter set by isothermal coupling parameters, an outer membrane mass transfer proportion coefficient, an in-hole mass transfer coefficient, a preset flow power law index and a maximum resin adsorption quantity, reconstructing an effective affinity coefficient, an outer membrane mass transfer coefficient and an overall mass transfer coefficient, and outputting a consistency judging result identifier.
  2. 2. The method for on-line identification of imidazolium resin adsorption kinetics parameters according to claim 1, wherein the steps of synchronously collecting flow, inlet water concentration, outlet water concentration, conductivity, temperature and ph, and obtaining apparent ionic strength from the conductivity according to a preset calibration relation, comprise: acquiring flow, water inlet concentration, water outlet concentration, conductivity, temperature and pH value at the same sampling moment, and generating an original data frame by taking the sampling moment as a uniform time mark; Obtaining apparent ion intensity from conductivity based on a preset calibration relation, wherein the calibration coefficient of the preset calibration relation is determined by linear fitting of preset conductivity calibration points corresponding to two known apparent ion intensities, the calibration coefficient comprises a proportion item and a bias item, the conductivity is read from an original data frame, a proportion result is obtained by multiplying the conductivity by the proportion item in the calibration coefficient, the apparent ion intensity is obtained by adding the proportion result and the bias item in the calibration coefficient, the apparent ion intensity is compared with zero, the apparent ion intensity is set to zero when the apparent ion intensity is smaller than zero, and the apparent ion intensity is written into the original data frame to obtain an expanded data frame.
  3. 3. The method for on-line identification of imidazolium resin adsorption kinetic parameters according to claim 2, wherein the mass balance is performed according to the flow rate, the water inlet concentration, the water outlet concentration and the mass of the resin dry basis to obtain a real-time track of the average adsorption amount of the resin, comprising: step 11, reading flow, inlet water concentration and outlet water concentration from the extended data frame, and determining the difference value between the inlet water concentration and the outlet water concentration as a concentration difference value; step 12, determining the product of the flow and the concentration difference as a removal amount in unit time, reading the dry basis mass of the resin, and determining the ratio of the removal amount in unit time to the dry basis mass of the resin as the average adsorption amount change rate of the resin; And step 13, calling a preset sampling time step, adding the product of the change rate of the resin average adsorption quantity and the preset sampling time step to the resin average adsorption quantity at the last sampling time to obtain the resin average adsorption quantity at the current sampling time, and collecting the resin average adsorption quantity at each sampling time into a real-time track of the resin average adsorption quantity.
  4. 4. The method for on-line identification of imidazolium resin adsorption kinetics parameters according to claim 2, wherein constructing a counter ion coupling isothermal driving force based on a maximum adsorption amount of the resin, a water outlet concentration, an apparent ion intensity and an effective affinity coefficient, and screening a quasi-equilibrium section according to a rate of change of an average adsorption amount of the resin, comprises: step 21, reading the water concentration and apparent ion intensity from the extended data frame, and reading the maximum adsorption capacity of the resin, wherein the isothermal coupling parameter comprises a first coupling coefficient and a first index coefficient, taking the product of the first index coefficient and the apparent ion intensity as an index, calculating an index operation result based on a natural constant, and multiplying the index operation result by the first coupling coefficient to obtain an effective affinity coefficient; Step 22, taking the product of the effective affinity coefficient and the concentration of the effluent as a molecule, taking the added result of the constant 1 and the product as a denominator, multiplying the maximum adsorption capacity of the resin by the ratio of the molecule to the denominator to obtain a counter ion coupling isothermal driving force, and collecting the counter ion coupling isothermal driving forces at each sampling moment to form a counter ion coupling isothermal driving force sequence; step 23, calculating the resin average adsorption quantity change rate based on the resin average adsorption quantity real-time track and a preset sampling time step, wherein the resin average adsorption quantity difference value at the adjacent sampling time is taken as a molecule, the preset sampling time step is taken as a denominator, and the ratio of the molecule to the denominator is calculated to obtain the resin average adsorption quantity change rate; And when the accumulated duration of the continuous candidate time is not less than a preset quasi-equilibrium duration threshold, determining a time interval corresponding to the continuous candidate time as a quasi-equilibrium section, outputting a time index set of the quasi-equilibrium section, a mean value of the resin average adsorption quantity section, a mean value of the water outlet concentration section and a mean value of the apparent ion intensity section in the quasi-equilibrium section, and calculating the accumulated duration by the product of the number of the continuous candidate time and the preset sampling time step.
  5. 5. The method for on-line identification of imidazolium resin adsorption kinetics parameters according to claim 4, wherein for the quasi-equilibrium segments corresponding to two different apparent ionic strengths, obtaining a parallel quasi-equilibrium relation between the average adsorption capacity of the resin and the water outlet concentration, and solving isothermal coupling parameters, comprises: Step 31, screening quasi-equilibrium sections with unequal average values of two apparent ion intensity sections from a quasi-equilibrium section set, respectively determining the quasi-equilibrium sections as a first quasi-equilibrium section and a second quasi-equilibrium section, and respectively obtaining average resin adsorption quantity section average values, effluent concentration section average values and apparent ion intensity section average values of the first quasi-equilibrium section and the second quasi-equilibrium section; Step 32, reading the maximum adsorption capacity of the resin, and calculating the effective affinity coefficient of the first quasi-equilibrium section and the second quasi-equilibrium section according to the average value of the apparent ion intensity sections of the first quasi-equilibrium section and the second quasi-equilibrium section in a mode of step 21 respectively, wherein the product of the effective affinity coefficient and the average value of the water outlet concentration section is taken as a molecule, the product of a constant 1 and the product is taken as a denominator, and the ratio of the molecule and the denominator is multiplied by the maximum adsorption capacity of the resin to obtain quasi-equilibrium relation formulas corresponding to the first quasi-equilibrium section and the second quasi-equilibrium section respectively; and 33, combining the average resin adsorption capacity section mean value of the first quasi-equilibrium section with the quasi-equilibrium relation corresponding to the first quasi-equilibrium section, combining the average resin adsorption capacity section mean value of the second quasi-equilibrium section with the quasi-equilibrium relation corresponding to the second quasi-equilibrium section, forming two equations about the first coupling coefficient and the first index coefficient, performing combined solution to obtain the first coupling coefficient and the first index coefficient, and writing the first coupling coefficient and the first index coefficient into isothermal coupling parameters.
  6. 6. The method for on-line identification of imidazolium resin adsorption kinetics parameters according to claim 4, wherein substituting isothermal coupling parameters into counter ion coupling isothermal driving force, and calculating an overall mass transfer coefficient point by point from an average adsorption amount of resin and the counter ion coupling isothermal driving force based on a linear driving force kinetic skeleton, comprises: Step 41, reading isothermal coupling parameters, reading apparent ion intensity and effluent concentration from an extended data frame, and reading the maximum adsorption capacity of resin, wherein the apparent ion intensity is taken as input, and the effective affinity coefficient is calculated according to the mode of step 21; Step 42, calculating the isothermal driving force of the counter ion coupling according to the mode of step 22 by taking the effective affinity coefficient, the water outlet concentration and the maximum adsorption capacity of the resin as inputs; And 43, reading the resin average adsorption quantity at adjacent sampling moments and a preset sampling time step, obtaining the resin average adsorption quantity change rate according to the calculation mode of the resin average adsorption quantity change rate in the step 23, taking the resin average adsorption quantity change rate as a numerator, taking a driving force difference value as a denominator, calculating the ratio of the numerator to the denominator to obtain an integral mass transfer coefficient, and skipping the integral mass transfer coefficient calculation at the corresponding sampling moment when the absolute value of the driving force difference value is smaller than a preset difference value threshold, and collecting the integral mass transfer coefficients at all the sampling moments to form an integral mass transfer coefficient sequence.
  7. 7. The method for on-line identification of imidazolium resin adsorption kinetics parameters according to claim 4, wherein screening a counter ion state stable section, sequentially setting two flows in the counter ion state stable section and obtaining corresponding overall mass transfer coefficients, establishing a resistance series equation by combining a preset flow power law index, solving an outer membrane mass transfer proportional coefficient and an in-hole mass transfer coefficient, and obtaining an outer membrane mass transfer coefficient, comprising: step 51, reading apparent ion intensity in the extended data frame, respectively determining the maximum value and the minimum value of the apparent ion intensity in a sliding time window of continuous sampling time, and determining the difference value of the maximum value and the minimum value as fluctuation amplitude; comparing the fluctuation amplitude with a preset apparent ion intensity fluctuation threshold value, and determining a corresponding time interval as a counter ion state stable segment and outputting a time index set of the counter ion state stable segment when the fluctuation amplitude is not more than the preset apparent ion intensity fluctuation threshold value and the accumulated duration is not less than a preset stable duration threshold value; Step 52, sequentially setting a first flow and a second flow in the counter ion state stabilizing section, and respectively obtaining overall mass transfer coefficients in a first flow holding section and a second flow holding section; arithmetic average is carried out on the integral mass transfer coefficients in the first flow holding interval to obtain a first integral mass transfer coefficient, arithmetic average is carried out on the integral mass transfer coefficients in the second flow holding interval to obtain a second integral mass transfer coefficient, and paired data of the first flow and the first integral mass transfer coefficient and paired data of the second flow and the second integral mass transfer coefficient are formed; And 53, reading a preset flow power law index, defining an outer membrane mass transfer coefficient as a power law function of an outer membrane mass transfer proportion coefficient and flow, expressing the reciprocal of an integral mass transfer coefficient as the sum of the reciprocal of the outer membrane mass transfer coefficient and the reciprocal of an in-hole mass transfer coefficient, substituting paired data of a first flow and the first integral mass transfer coefficient and paired data of a second flow and the second integral mass transfer coefficient into the relation between the power law function and the reciprocal to form two equations related to the outer membrane mass transfer proportion coefficient and the in-hole mass transfer coefficient, solving in parallel to obtain the outer membrane mass transfer proportion coefficient and the in-hole mass transfer coefficient, and substituting the first flow and the second flow into the power law function to calculate the outer membrane mass transfer coefficient.
  8. 8. The method for on-line identification of imidazolium resin adsorption kinetics parameters according to claim 7, wherein the isothermal coupling parameters, the outer membrane mass transfer scaling factor, the in-hole mass transfer factor, the preset flow power law index and the maximum resin adsorption capacity are combined into a core parameter set, the effective affinity factor, the outer membrane mass transfer factor and the overall mass transfer factor are reconstructed, and a consistency judgment result identifier is output, and the method comprises the following steps: Step 61, reading isothermal coupling parameters, reading an outer membrane mass transfer proportion coefficient, an inner hole mass transfer coefficient, a preset flow power law index and a maximum resin adsorption capacity, and forming a core parameter set by the first coupling coefficient, the first index coefficient, the outer membrane mass transfer proportion coefficient, the inner hole mass transfer coefficient, the preset flow power law index and the maximum resin adsorption capacity according to a fixed field sequence; Step 62, reading apparent ion intensity and flow from the expanded data frame at each sampling moment, and reading a first coupling coefficient, a first index coefficient, an outer membrane mass transfer proportion coefficient, an in-hole mass transfer coefficient and a preset flow power law index from a core parameter set, wherein the apparent ion intensity is used as input, an effective affinity coefficient is calculated according to the mode of step 21, the outer membrane mass transfer proportion coefficient, the preset flow power law index and the flow are used as input, the outer membrane mass transfer coefficient is obtained according to the mode of calculating the outer membrane mass transfer coefficient in step 53, and the outer membrane mass transfer coefficient and the in-hole mass transfer coefficient are used as input, so that the overall mass transfer coefficient is obtained according to the reciprocal sum relation of the overall mass transfer coefficient in step 53; And 63, reading a repeated solution result set of mass transfer coefficients in the hole in the stable segment of the counter ion state, calculating a variation coefficient of the repeated solution result set and comparing the variation coefficient with a preset variation coefficient threshold value to obtain a hole mass transfer consistency judgment, reading the apparent ion strength and the effective affinity coefficient in the same stable segment of the counter ion state, checking the response relation that the effective affinity coefficient is not increased when the apparent ion strength is increased point by point to obtain a response consistency judgment, and outputting a consistency judgment result mark as passing when the hole mass transfer consistency judgment is passed and the response consistency judgment is passed, or else outputting a consistency judgment result mark as not passing.
  9. 9. The method for on-line identification of imidazolium resin adsorption kinetics parameters according to claim 8, wherein the in-pore mass transfer consistency determination comprises: Step 71, in the same counter ion state stable section, according to the simultaneous solving process of step 53, carrying out simultaneous solving of the external film mass transfer proportion coefficient and the in-hole mass transfer coefficient for preset times, wherein each simultaneous solving uses the same preset flow power law index and the paired data of the first flow and the first integral mass transfer coefficient and the paired data of the second flow and the second integral mass transfer coefficient in the same counter ion state stable section, and sequentially writes the in-hole mass transfer coefficient obtained by each simultaneous solving into a repeated solving result set of the in-hole mass transfer coefficient; Step 72, calculating a mean value and a standard deviation for the repeated solution result set of the in-hole mass transfer coefficients, wherein the mean value is the ratio of the sum result of all in-hole mass transfer coefficients in the repeated solution result set of the in-hole mass transfer coefficients to the number of elements of the repeated solution result set of the in-hole mass transfer coefficients, and the standard deviation is the square root of the ratio of the sum result of the square difference value of each in-hole mass transfer coefficient and the mean value in the repeated solution result set of the in-hole mass transfer coefficients to the number of elements of the repeated solution result set of the in-hole mass transfer coefficients; And 73, determining the ratio of the standard deviation to the mean value as a variation coefficient, comparing the variation coefficient with a preset variation coefficient threshold, determining that the in-hole mass transfer consistency is judged to pass when the variation coefficient is not larger than the preset variation coefficient threshold, and determining that the in-hole mass transfer consistency is not judged to pass when the variation coefficient is larger than the preset variation coefficient threshold.
  10. 10. An imidazolium resin adsorption kinetics parameter on-line identification system, characterized in that an imidazolium resin adsorption kinetics parameter on-line identification method as claimed in any one of claims 1 to 9 is adopted, comprising: The data acquisition module is used for synchronously acquiring flow, water inlet concentration, water outlet concentration, conductivity, temperature and pH value, and obtaining apparent ionic strength from the conductivity according to a preset calibration relation; The mass balance module is used for carrying out mass balance according to the flow, the inflow water concentration, the outflow water concentration and the mass of the resin dry basis to obtain a real-time track of the average adsorption quantity of the resin; The isothermal driving module is used for constructing a counter ion coupling isothermal driving force based on the maximum adsorption capacity, the water outlet concentration, the apparent ion strength and the effective affinity coefficient of the resin, and screening a quasi-equilibrium section according to the change rate of the average adsorption capacity of the resin; The isothermal solving module is used for obtaining a parallel quasi-equilibrium relation between the average adsorption capacity of the resin and the water outlet concentration for the quasi-equilibrium sections corresponding to the two different apparent ionic strengths, and solving isothermal coupling parameters; the integral mass transfer module is used for substituting the isothermal coupling parameter into the counter ion coupling isothermal driving force, and calculating the integral mass transfer coefficient point by point based on the linear driving force dynamic skeleton by the resin average adsorption quantity and the counter ion coupling isothermal driving force; the resistance decoupling module is used for screening a counter ion state stable section, sequentially setting two-gear flow in the counter ion state stable section, acquiring a corresponding integral mass transfer coefficient, establishing a resistance series equation by combining a preset flow power law index, solving an outer membrane mass transfer proportional coefficient and an in-hole mass transfer coefficient, and acquiring an outer membrane mass transfer coefficient; and the parameter reconstruction module is used for forming a core parameter set from the isothermal coupling parameter, the outer membrane mass transfer proportion coefficient, the in-hole mass transfer coefficient, the preset flow power law index and the maximum resin adsorption quantity, reconstructing the effective affinity coefficient, the outer membrane mass transfer coefficient and the integral mass transfer coefficient, and outputting a consistency judgment result identifier.

Description

Online identification method and system for imidazolium resin adsorption kinetic parameters Technical Field The invention belongs to the technical field of adsorption detection, and particularly relates to an on-line identification method and system for adsorption kinetic parameters of imidazolium resin. Background The imidazolium resin is used as an adsorption material with ionic groups, the adsorption process is not only influenced by working conditions such as water inlet and outlet concentration and flow, but also can cause synchronous change of isothermal affinity characteristics and mass transfer process along with the change of solution ion environment. In the actual adsorption column operation, the fluctuation of the counter ion or ion intensity easily causes the grouping linkage drift of isothermal affinity parameters and mass transfer/diffusion parameters, and the weight switching of outer membrane mass transfer and in-hole diffusion is accompanied, so that the dynamic parameters are not kept constant under different working conditions. In the prior art, adsorption kinetic parameters are usually obtained by means of offline isothermal experiments or batch fitting, or the kinetic behavior is simply reduced to a single rate constant when modeling online, and the parameters are assumed to be stable during the running period. The method is easy to generate the problems of unrecognizable, multi-solution and parameter jump along with working conditions under the scene of obvious change of the ion environment, so that the online analysis result is difficult to stably multiplex and form a consistent data link with online detection data. Disclosure of Invention The invention provides an on-line identification method and system for adsorption kinetic parameters of imidazolium resin, which solve the technical problems that adsorption isothermal parameters and mass transfer parameters are difficult to identify synchronously under the condition of ion environment fluctuation, on-line calculation results of the kinetic parameters are unstable, and a consistency association mechanism is lacked between on-line detection data and a parameter model in the related technology. The invention provides an on-line identification method for the adsorption kinetic parameters of imidazolium resin, which comprises the following steps: Step 1, synchronously collecting flow, inlet water concentration, outlet water concentration, conductivity, temperature and pH value, and obtaining apparent ionic strength from the conductivity according to a preset calibration relation; step 2, carrying out mass balance calculation according to the flow, the inflow water concentration, the outflow water concentration and the resin dry basis mass to obtain a real-time track of the resin average adsorption quantity; Step 3, constructing a counter ion coupling isothermal driving force based on the maximum adsorption capacity, the effluent concentration, the apparent ion intensity and the effective affinity coefficient of the resin, and screening a quasi-equilibrium section according to the change rate of the average adsorption capacity of the resin; Step 4, for the quasi-equilibrium sections corresponding to two different apparent ionic strengths, obtaining a parallel quasi-equilibrium relation between the average adsorption capacity of the resin and the water outlet concentration, and solving isothermal coupling parameters; step 5, substituting isothermal coupling parameters into the counter ion coupling isothermal driving force, and calculating an overall mass transfer coefficient point by point based on the linear driving force dynamic skeleton by the resin average adsorption quantity and the counter ion coupling isothermal driving force; Step 6, screening a counter ion state stable section, sequentially setting two-gear flow in the counter ion state stable section, acquiring a corresponding integral mass transfer coefficient, establishing a resistance series equation by combining a preset flow power law index, solving an outer membrane mass transfer proportional coefficient and an in-hole mass transfer coefficient, and acquiring an outer membrane mass transfer coefficient; And 7, forming a core parameter set by isothermal coupling parameters, an outer membrane mass transfer proportion coefficient, an in-hole mass transfer coefficient, a preset flow power law index and a maximum resin adsorption quantity, reconstructing an effective affinity coefficient, an outer membrane mass transfer coefficient and an overall mass transfer coefficient, and outputting a consistency judging result identifier. The invention also provides an on-line identification system for the adsorption kinetic parameters of the imidazolium resin, which comprises the following steps: The data acquisition module is used for synchronously acquiring flow, water inlet concentration, water outlet concentration, conductivity, temperature and pH value, and obtaining apparent ionic