CN107500388A - The control method and device of electrical conductivity in a kind of heavy metal wastewater thereby electrochemical treatment process - Google Patents

The control method and device of electrical conductivity in a kind of heavy metal wastewater thereby electrochemical treatment process Download PDF

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CN107500388A
CN107500388A CN201710723539.3A CN201710723539A CN107500388A CN 107500388 A CN107500388 A CN 107500388A CN 201710723539 A CN201710723539 A CN 201710723539A CN 107500388 A CN107500388 A CN 107500388A
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mrow
msub
heavy metal
metal ion
concentration
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CN107500388B (en
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阳春华
张凤雪
朱红求
李勇刚
桂卫华
陈俊名
李繁飙
王强
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Central South University
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104Devices therefor; Their operating or servicing
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/20Heavy metals or heavy metal compounds
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02DCLIMATE CHANGE MITIGATION TECHNOLOGIES IN INFORMATION AND COMMUNICATION TECHNOLOGIES [ICT], I.E. INFORMATION AND COMMUNICATION TECHNOLOGIES AIMING AT THE REDUCTION OF THEIR OWN ENERGY USE
    • Y02D10/00Energy efficient computing, e.g. low power processors, power management or thermal management

Abstract

The present invention provides a kind of control method and device of electrical conductivity in heavy metal wastewater thereby electrochemical treatment process, and this method is:Establish the heavy metal ion molar concentration mass balance model with time lag;Based on the heavy metal ion molar concentration mass balance model with time lag, power consumption Optimized model in heavy metal wastewater thereby electrochemical treatment process is established so that power consumption is minimum in the case that in outlet, concentration of heavy metal ion meets predetermined threshold value;Obtain the detection data of the entrance concentration of heavy metal ion of the electrolysis pending waste water of trough pool, solution is optimized to power consumption Optimized model adoption status branching algorithm, obtain so that the best electrical conductivity numerical value in the case that concentration of heavy metal ion meets predetermined threshold value is exported, so as to calculate Na needed for pretreatment process2SO4Addition.Electrical conductivity control method provided by the invention, can coordinate to control pretreatment process and electrowinning process, carry out real-time monitoring to electrical conductivity, the optimization to electrochemical wastewater processing procedure is instructed significant.

Description

The control method and device of electrical conductivity in a kind of heavy metal wastewater thereby electrochemical treatment process
Technical field
The present invention relates to electrochemical technology field, more particularly, in a kind of heavy metal wastewater thereby electrochemical treatment process The control method and device of electrical conductivity.
Background technology
Industrial wastewater has turned into the important pollution sources of water pollution, is mainly derived from the production process of factories and miness.Heavy metal pollution Thing especially a kind of heavy metal contaminants such as cadmium, cobalt, nickel have a significant damages such as carcinogenic teratogenesis, and China is heavy metal-polluted to this one kind The discharge of dye thing also has strict standard.Electrochemistry further treatment technique efficiency high, easy to operate and environmental compatible, can The effective heavy metal ion gone in water removal.It is stronger by impressed current, the regulation reaction condition at any time of voltage, controllability; Electronics transfer only is carried out between electrode and waste water component, be not required to add reductant-oxidant in addition, avoid due to add medicament and Caused secondary pollution problem, while have air supporting, flocculation, disinfective action concurrently again.
Electrochemical techniques processing heavy metal wastewater thereby process is made up of pretreatment process and electrowinning process, and electrical conductivity is to influence to give up An important factor for water treatment efficiency, and electrical conductivity needs to be adjusted optimally just can guarantee that electrolysis work in advance in pretreatment process Sequence reaches best treatment effect.But very big time lag from pretreatment process to electrowinning process be present in solution, and at this During battery lead plate constantly dissolving causes pole plate spacing constantly to become big, the change for being electrolysed slot status causes electrochemical reaction speed The change of rate, so as to cause electrical conductivity regulation difficult, and then influence the treatment effect of outlet concentration of heavy metal ion.
During actual electrochemical treatment of wastewater, the setting of electrical conductivity is often judged according to artificial experience, and simultaneously The problem of waste water flows to the time lag of electrolytic cell, battery lead plate consumption and electric energy optimizing from pretreatment process is not considered, ignores electricity Influence of the groove running status to electrochemical reaction efficiency is solved, it is poor that this results in heavy metal containing wastewater treatment effect, energy waste.
The content of the invention
In order to overcome the above-mentioned problems in the prior art at least in part, the present invention provides a kind of heavy metal wastewater thereby electricity The control method and device of electrical conductivity in chemical treating process.
According to an aspect of the present invention, the present invention provides electrical conductivity in a kind of heavy metal wastewater thereby electrochemical treatment process Control method, including:S1, mass conservation law and Faraday's law based on Flow of Goods and Materials, establish the heavy metal with time lag from Sub- molar concentration mass balance model;S2, based on the heavy metal ion molar concentration mass balance model with time lag, establish Power consumption Optimized model in heavy metal wastewater thereby electrochemical treatment process so that concentration of heavy metal ion meets default threshold in outlet Power consumption is minimum in the case of value;S3, obtain the testing number of the entrance concentration of heavy metal ion of the electrolysis pending waste water of trough pool According to optimizing solution to the power consumption Optimized model adoption status branching algorithm, obtain so that exporting heavy metal ion Concentration meet predetermined threshold value in the case of best electrical conductivity numerical value, so as to calculate Na needed for pretreatment process2SO4Addition Amount.
Wherein, the heavy metal ion molar concentration mass balance model with time lag is specially:
Wherein,It is the molar concentration rate of change of heavy metal ion A in electrolytic cell;It is heavy metal ion A Entrance molar concentration;τ is the time required to electrolyte flows to electrolytic cell from pretreatment process;CA(t) be in electrolytic cell heavy metal from Sub- A molar concentration;F is the flow of entrance solution;V is the volume of electrolytic cell;rAIt is the electrification of heavy metal ion A in electrolytic cell Learn reaction rate.
Wherein, the kinetic model of heavy metal ion A electrochemical reaction speed is specially in the electrolytic cell:
Wherein, S is polar plate area;U is decomposition voltage;κ is electrical conductivity;Z is the charge number of electrode reaction transfer, is taken just Value;F is Faraday constant;L0For the initial spacing of pole plate;R is iron atom radius;V is the volume of electrolytic cell;NAIt is Avobenzene gal moral Sieve constant;It is the initial molar concentration of A ions;β1It is parameter to be identified;J is electrolytic current density.
Wherein, the power consumption Optimized model is specially:
Wherein, W is power consumption;M is minus plate number;S is every piece of minus plate area;U is tank voltage;t0And tfRespectively Electrolysis starts the time with terminating;It is outlet heavy metal ion A concentration;J is current density;κ is electrical conductivity;L is pole plate Spacing;It is the desired value that wastewater outlet heavy metal ion A concentration should reach;UmaxOn the voltage that can bear for battery lead plate Limit.
Wherein, the tank voltage U in the power consumption Optimized model and concentration of heavy metal ion CA, between current density, J Relation be specially:
Wherein,It is the equilibrium potential constant of A elemental releases;V is the volume of electrolytic cell;S is polar plate area;R is heating power Learn constant;F is Faraday constant;It is the initial molar concentration of A ions;L0For the initial spacing of pole plate;T is electrolysis temperature;r It is the activity coefficient of A ions;MAIt is heavy metal A relative atomic weight;α15For parameter to be identified.
Wherein, Na needed for pretreatment process is calculated in the S32SO4Addition concretely comprise the following steps:
S31, the molar conductivity of solution can be obtained according to Cole Lao Wushi empirical equations, and be calculated and work as electrical conductivity For κ when Na2SO4Molar concentration:
Wherein,For Na2SO4The molar conductivity of solution, the relation with electrical conductivity κ areCαFor Na2SO4 Molar concentration;For Na2SO4The limiting molar conductivity of solution, is typically obtained by extrapolation;β is constant;
S32, according to the Na2SO4Molar concentration, calculate required Na2SO4Addition, calculation formula is specially:
mα=CαMαV
Wherein, mαFor required Na2SO4Addition quality;MαFor Na2SO4Molal weight;V is electrolytic cell volume.
According to another aspect of the present invention, the present invention provides electrical conductivity in a kind of heavy metal wastewater thereby electrochemical treatment process Control device, including:First model establishes unit, for mass conservation law and Faraday's law based on Flow of Goods and Materials, Establish the heavy metal ion molar concentration mass balance model with time lag;Second model establishes unit, during for based on the band Stagnant heavy metal ion molar concentration mass balance model, establish power consumption in heavy metal wastewater thereby electrochemical treatment process and optimize Model so that power consumption is minimum in the case that concentration of heavy metal ion meets predetermined threshold value in outlet;Control unit, for obtaining The detection data of the entrance concentration of heavy metal ion of the pending waste water of power taking solution trough pool, the power consumption Optimized model is used State branching algorithm optimizes solution, obtain so that export concentration of heavy metal ion meet it is optimal in the case of predetermined threshold value Conductivity values, so as to calculate Na needed for pretreatment process2SO4Addition.
Wherein, including:First computing unit, for mole electricity of solution can be obtained according to Cole Lao Wushi empirical equations Conductance, and the Na when electrical conductivity is κ is calculated2SO4Molar concentration:
Wherein,For Na2SO4The molar conductivity of solution, the relation with electrical conductivity κ areCαFor Na2SO4 Molar concentration;For Na2SO4The limiting molar conductivity of solution;β is constant;
Second computing unit, for according to the Na2SO4Molar concentration, calculate required Na2SO4Addition, meter Calculating formula is specially:
mα=CαMαV
Wherein, mαFor required Na2SO4Addition quality;MαFor Na2SO4Molal weight;V is electrolytic cell volume.
Wherein, first model establishes the heavy metal ion molar concentration mass balance model with time lag of unit foundation Specially:
Wherein,It is the molar concentration rate of change of heavy metal ion A in electrolytic cell;It is heavy metal ion A Entrance molar concentration;τ is the time required to electrolyte flows to electrolytic cell from pretreatment process;CA(t) be in electrolytic cell heavy metal from Sub- A molar concentration;F is the flow of entrance solution;V is the volume of electrolytic cell;rAIt is the electrification of heavy metal ion A in electrolytic cell Learn reaction rate.
Wherein, second model establish unit foundation power consumption Optimized model be specially:
Wherein, W is power consumption;M is minus plate number;S is every piece of minus plate area;U is tank voltage;t0And tfRespectively Electrolysis starts the time with terminating;It is outlet heavy metal ion A concentration;J is current density;κ is electrical conductivity;L is between pole plate Away from;It is the desired value that wastewater outlet heavy metal ion A concentration should reach;UmaxThe upper voltage limit that can bear for battery lead plate.
To sum up, in heavy metal wastewater thereby electrochemical treatment process provided by the invention electrical conductivity control method, when establishing band Stagnant heavy metal ion molar concentration mass balance model;Based on the heavy metal ion molar concentration mass balance mould with time lag Type, establish power consumption Optimized model in heavy metal wastewater thereby electrochemical treatment process so that concentration of heavy metal ion is expired in outlet Power consumption is minimum in the case of sufficient predetermined threshold value;Obtain the inspection of the entrance concentration of heavy metal ion of the electrolysis pending waste water of trough pool Data are surveyed, solution is optimized to power consumption Optimized model adoption status branching algorithm, obtained so that exporting heavy metal ion Concentration meet predetermined threshold value in the case of best electrical conductivity numerical value, so as to calculate Na needed for pretreatment process2SO4Addition Amount.The control method of electrical conductivity, can coordinate to control pre- place in the heavy metal wastewater thereby electrochemical treatment process that the present embodiment provides Science and engineering sequence and electrowinning process, real-time monitoring is carried out to electrical conductivity, the optimization to electrochemical wastewater processing procedure is instructed with important Meaning.
Brief description of the drawings
Fig. 1 is the control method of electrical conductivity in a kind of heavy metal wastewater thereby electrochemical treatment process according to the embodiment of the present invention Flow chart;
Fig. 2 is the outlet concentration of heavy metal ion curve synoptic diagram according to the embodiment of the present invention;
Fig. 3 is the control device of electrical conductivity in a kind of heavy metal wastewater thereby electrochemical treatment process according to the embodiment of the present invention Structured flowchart.
Embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with accompanying drawing, to the embodiment of the present invention In technical scheme be explicitly described, it is clear that described embodiment is part of the embodiment of the present invention, rather than all Embodiment.Based on the embodiment in the present invention, those of ordinary skill in the art institute under the premise of creative work is not made The every other embodiment obtained, belongs to the scope of protection of the invention.
Fig. 1 is the control method of electrical conductivity in a kind of heavy metal wastewater thereby electrochemical treatment process according to the embodiment of the present invention Flow chart, as shown in figure 1, including:
S1, mass conservation law and Faraday's law based on Flow of Goods and Materials, establishes the heavy metal ion mole with time lag Concentration mass balance model;
The mass conservation law and Faraday's law of Flow of Goods and Materials in chemical production processes are preferably based on, establishes reflection A band time lag huge sum of money for relation between electrolytic cell heavy metals ion concentration, conductivity of waste water, pole plate spacing and current density Belong to ion molar concentration mass balance model.
S2, based on the heavy metal ion molar concentration mass balance model with time lag, establish heavy metal wastewater thereby electrification Learn power consumption Optimized model in processing procedure so that electric energy in the case that concentration of heavy metal ion meets predetermined threshold value in outlet Consumption is minimum;
Preferably, establish and reached using the minimum target of power consumption, electrical conductivity as controlled quentity controlled variable and outlet concentration of heavy metal ion It is designated as the electrochemical reaction process electric energy optimizing model of constraints so that concentration of heavy metal ion meets predetermined threshold value in outlet In the case of power consumption it is minimum;
S3, the detection data of the entrance concentration of heavy metal ion of the electrolysis pending waste water of trough pool are obtained, the electric energy is disappeared Consumption Optimized model adoption status branching algorithm optimizes solution, obtains so that exporting concentration of heavy metal ion meets predetermined threshold value In the case of best electrical conductivity numerical value, so as to calculate Na needed for pretreatment process2SO4Addition.
Wherein, electrochemical techniques processing heavy metal wastewater thereby process is made up of pretreatment process and electrowinning process.
Preferably, solving to obtain using power consumption Optimized model causes outlet concentration of heavy metal ion to meet predetermined threshold value In the case of best electrical conductivity numerical value, so as to provide foundation for regulation electrical conductivity, with stabilization of export concentration of heavy metal ion, save About electric energy and raw material resources.
A kind of control method of electrical conductivity in heavy metal wastewater thereby electrochemical treatment process is present embodiments provided, when establishing band Stagnant heavy metal ion molar concentration mass balance model;Based on the heavy metal ion molar concentration mass balance mould with time lag Type, establish power consumption Optimized model in heavy metal wastewater thereby electrochemical treatment process so that concentration of heavy metal ion is expired in outlet Power consumption is minimum in the case of sufficient predetermined threshold value;Obtain the inspection of the entrance concentration of heavy metal ion of the electrolysis pending waste water of trough pool Data are surveyed, solution is optimized to power consumption Optimized model adoption status branching algorithm, obtained so that exporting heavy metal ion Concentration meet predetermined threshold value in the case of best electrical conductivity numerical value, so as to calculate Na needed for pretreatment process2SO4Addition Amount.The control method of electrical conductivity, can coordinate to control pre- place in the heavy metal wastewater thereby electrochemical treatment process that the present embodiment provides Science and engineering sequence and electrowinning process, real-time monitoring is carried out to electrical conductivity, the optimization to electrochemical wastewater processing procedure is instructed with important Meaning.
In another embodiment of the present invention, on the basis of above-described embodiment, the heavy metal ion with time lag Molar concentration mass balance model is specially:
Wherein,It is the molar concentration rate of change of heavy metal ion A in electrolytic cell;It is heavy metal ion A Entrance molar concentration;τ is the time required to electrolyte flows to electrolytic cell from pretreatment process;CA(t) be in electrolytic cell heavy metal from Sub- A molar concentration;F is the flow of entrance solution;V is the volume of electrolytic cell;rAIt is the electrification of heavy metal ion A in electrolytic cell Learn reaction rate.
Preferably, by heavy metal ion molar concentration mass balance model with time lag obtain in electrolytic cell heavy metal from Sub- A molar concentration rate of change.
In yet another embodiment of the present invention, on the basis of above-described embodiment, heavy metal ion A in the electrolytic cell The kinetic model of electrochemical reaction speed be specially:
Wherein, S is polar plate area;U is decomposition voltage;κ is electrical conductivity;Z is the charge number of electrode reaction transfer, is taken just Value;F is Faraday constant;L0For the initial spacing of pole plate;R is iron atom radius;V is the volume of electrolytic cell;NAIt is Avobenzene gal moral Sieve constant;It is the initial molar concentration of A ions;β1It is parameter to be identified;J is electrolytic current density.
Preferably, the kinetic model of heavy metal ion A electrochemical reaction speed is foundation with time lag in electrolytic cell Heavy metal ion molar concentration mass balance model provides foundation.
In yet another embodiment of the present invention, on the basis of above-described embodiment, the power consumption Optimized model tool Body is:
Wherein, W is power consumption;M is minus plate number;S is every piece of minus plate area;U is tank voltage;t0And tfRespectively Electrolysis starts the time with terminating;It is outlet heavy metal ion A concentration;J is current density;κ is electrical conductivity;L is between pole plate Away from;It is the desired value that wastewater outlet heavy metal ion A concentration should reach;UmaxThe upper voltage limit that can bear for battery lead plate.
Preferably, establish and reached using the minimum target of power consumption, electrical conductivity as controlled quentity controlled variable and outlet concentration of heavy metal ion It is designated as the electrochemical reaction process power consumption Optimized model of constraints so that concentration of heavy metal ion meets default in outlet The excellent minimum of power consumption in the case of threshold value.
In another embodiment of the invention, on the basis of above-described embodiment, in the power consumption Optimized model Tank voltage U and concentration of heavy metal ion CA, the relation between current density, J be specially:
Wherein,It is the equilibrium potential constant of A elemental releases;V is the volume of electrolytic cell;S is polar plate area;R is thermodynamics Constant;F is Faraday constant;It is the initial molar concentration of A ions;L0For the initial spacing of pole plate;T is electrolysis temperature;R is The activity coefficient of A ions;MAIt is heavy metal A relative atomic weight;α15For parameter to be identified.
Preferably, tank voltage U and concentration of heavy metal ion CA, relational expression between current density, J is establishes electric energy Consume Optimized model and foundation is provided.
In another embodiment of the invention, on the basis of above-described embodiment, calculated in the S3 in pretreatment process Required Na2SO4Addition concretely comprise the following steps:
S31, the molar conductivity of solution can be obtained according to Cole Lao Wushi empirical equations, and be calculated and work as electrical conductivity For κ when Na2SO4Molar concentration:
Wherein,For Na2SO4The molar conductivity of solution, the relation with electrical conductivity κ areCαFor Na2SO4's Molar concentration;For Na2SO4The limiting molar conductivity of solution;β is constant;
S32, according to the Na2SO4Molar concentration, calculate required Na2SO4Addition, calculation formula is specially:
mα=CαMαV
Wherein, mαFor required Na2SO4Addition quality;MαFor Na2SO4Molal weight;V is electrolytic cell volume.
Preferably, by calculating Na needed for pretreatment process2SO4Addition, can cause outlet heavy metal ion Concentration meets the excellent minimum of power consumption in the case of predetermined threshold value, saves material simultaneously.
The method provided below with a specific example above-described embodiment is explained.
For a kind of pending heavy metal industrial effluent containing antimony, wherein antimony content is 180mg/L, electrical conductivity 1.06s/m, Continuum micromeehanics mode is taken, flow is controlled in 55m3/h, and the time that waste water flows to electrolytic cell from pretreatment tank is 10min.Using The heavy metal wastewater thereby electrochemical treatment process electrical conductivity control method dynamic realtime that above-described embodiment provides adjusts pending waste water Conductivity value so that antimony ion concentration is up to standard arrives 0.5mg/L for outlet.The first step, based on Flow of Goods and Materials in chemical production processes Mass conservation law and Faraday's law structure the heavy metal ion molar concentration mass balance model with time lag;Second step, Establish using the minimum target of power consumption, electrical conductivity as controlled quentity controlled variable and the outlet concentration of heavy metal ion electricity up to standard for constraints Chemical reaction process electric energy optimizing model so that power consumption in the case that concentration of heavy metal ion meets predetermined threshold value in outlet It is minimum;3rd step, obtain the detection data of the entrance concentration of heavy metal ion of the electrolysis pending waste water of trough pool, adoption status transfer Algorithm optimizes solution, obtains so that exporting the best electrical conductivity value in the case that concentration of heavy metal ion meets predetermined threshold value And calculate Na needed for preprocessing process2SO4Addition.
Using heavy metal wastewater thereby electrochemical treatment process electrical conductivity control method, the electrical conductivity of 24 hours is controlled, And contrasted using the method for manual adjustment, the Na that two methods obtain2SO4Addition and power consumption contrast, such as table 1 Shown, outlet antimony ion concentration is as shown in Figure 2.From table 1 and Fig. 2, using heavy metal wastewater thereby electrochemical treatment process conductance Rate control method can be coordinated to control preprocessing process and electrochemical process, carry out real-time monitoring to electrical conductivity so that go out salty In the case that concentration of metal ions meets predetermined threshold value, optimize Na2SO4Addition.
The Na of table 12SO4Addition and power consumption contrast
Manual operation Optimal control operates
Na2SO4Addition (kg) 2400 2290.6
Power consumption (kWh) 1390.09 1263.2
A kind of control method of electrical conductivity in heavy metal wastewater thereby electrochemical treatment process is present embodiments provided, can be coordinated Pretreatment process and electrowinning process are controlled, real-time monitoring is carried out to electrical conductivity, the optimization for electrochemical wastewater processing procedure refers to Lead significant.
Fig. 3 is the control device of electrical conductivity in a kind of heavy metal wastewater thereby electrochemical treatment process according to the embodiment of the present invention Structured flowchart, as shown in figure 3, including:First model establishes unit 301, the second model establishes unit 302 and control unit 303;Wherein,
First model establishes unit 301 and is used for mass conservation law and Faraday's law based on Flow of Goods and Materials, establishes band The heavy metal ion molar concentration mass balance model of time lag;
The mass conservation law and Faraday's law of Flow of Goods and Materials in chemical production processes are preferably based on, establishes reflection A band time lag huge sum of money for relation between electrolytic cell heavy metals ion concentration, conductivity of waste water, pole plate spacing and current density Belong to ion molar concentration mass balance model.
Second model is established unit 302 and is used for based on the heavy metal ion molar concentration mass balance mould with time lag Type, establish power consumption Optimized model in heavy metal wastewater thereby electrochemical treatment process so that concentration of heavy metal ion is expired in outlet Power consumption is minimum in the case of sufficient predetermined threshold value;
Preferably, establish and reached using the minimum target of power consumption, electrical conductivity as controlled quentity controlled variable and outlet concentration of heavy metal ion It is designated as the electrochemical reaction process electric energy optimizing model of constraints so that concentration of heavy metal ion meets predetermined threshold value in outlet In the case of power consumption it is minimum;
Control unit 303 is used for the detection data for obtaining the entrance concentration of heavy metal ion of the electrolysis pending waste water of trough pool, Solution is optimized to the power consumption Optimized model adoption status branching algorithm, obtained so that exporting concentration of heavy metal ion Meet the best electrical conductivity numerical value in the case of predetermined threshold value, so as to calculate Na needed for pretreatment process2SO4Addition.
Preferably, solving to obtain using power consumption Optimized model causes outlet concentration of heavy metal ion to meet predetermined threshold value In the case of best electrical conductivity numerical value, so as to provide foundation for regulation electrical conductivity, with stabilization of export concentration of heavy metal ion, save About electric energy and raw material resources.
Present embodiments provide a kind of control device of electrical conductivity in heavy metal wastewater thereby electrochemical treatment process, the first model Unit is established, establishes the heavy metal ion molar concentration mass balance model with time lag;Second model establishes unit, during based on band Stagnant heavy metal ion molar concentration mass balance model, establish power consumption in heavy metal wastewater thereby electrochemical treatment process and optimize Model so that power consumption is minimum in the case that concentration of heavy metal ion meets predetermined threshold value in outlet;Control unit, obtain electricity The detection data of the entrance concentration of heavy metal ion of the pending waste water of trough pool are solved, power consumption Optimized model adoption status is shifted Algorithm optimizes solution, obtains so that exporting the best electrical conductivity number in the case that concentration of heavy metal ion meets predetermined threshold value Value, so as to calculate Na needed for pretreatment process2SO4Addition.The heavy metal wastewater thereby electrochemical treatments mistake that the present embodiment provides It the control device of electrical conductivity in journey, can coordinate to control pretreatment process and electrowinning process, real-time monitoring is carried out to electrical conductivity, it is right The optimization of electrochemical wastewater processing procedure is instructed significant.
In another embodiment of the invention, on the basis of above-described embodiment, including:
First computing unit, for the molar conductivity of solution can be obtained according to Cole Lao Wushi empirical equations, and count Calculation obtains the Na when electrical conductivity is κ2SO4Molar concentration:
Wherein,For Na2SO4The molar conductivity of solution, the relation with electrical conductivity κ areCαFor Na2SO4's Molar concentration;For Na2SO4The limiting molar conductivity of solution, is typically obtained by extrapolation;β is constant;
Second computing unit, for according to the Na2SO4Molar concentration, calculate required Na2SO4Addition, meter Calculating formula is specially:
mα=CαMαV
Wherein, mαFor required Na2SO4Addition quality;MαFor Na2SO4Molal weight;V is electrolytic cell volume.
Preferably, by calculating Na needed for pretreatment process2SO4Addition, can cause outlet heavy metal ion Concentration meets the excellent minimum of power consumption in the case of predetermined threshold value, saves material simultaneously.
In another embodiment of the invention, on the basis of above-described embodiment, first model establishes unit foundation The heavy metal ion molar concentration mass balance model with time lag be specially:
Wherein,It is the molar concentration rate of change of heavy metal ion A in electrolytic cell;It is heavy metal ion A Entrance molar concentration;τ is the time required to electrolyte flows to electrolytic cell from pretreatment process;CA(t) be in electrolytic cell heavy metal from Sub- A molar concentration;F is the flow of entrance solution;V is the volume of electrolytic cell;rAIt is the electrification of heavy metal ion A in electrolytic cell Learn reaction rate.
Preferably, by heavy metal ion molar concentration mass balance model with time lag obtain in electrolytic cell heavy metal from Sub- A molar concentration rate of change.
In another embodiment of the invention, on the basis of above-described embodiment, second model establishes unit foundation Power consumption Optimized model be specially:
Wherein, W is power consumption;M is minus plate number;S is every piece of minus plate area;U is tank voltage;t0And tfRespectively Electrolysis starts the time with terminating;It is outlet heavy metal ion A concentration;J is current density;κ is electrical conductivity;L is between pole plate Away from;It is the desired value that wastewater outlet heavy metal ion A concentration should reach;UmaxThe upper voltage limit that can bear for battery lead plate.
Preferably, establish and reached using the minimum target of power consumption, electrical conductivity as controlled quentity controlled variable and outlet concentration of heavy metal ion It is designated as the electrochemical reaction process power consumption Optimized model of constraints so that concentration of heavy metal ion meets default in outlet The excellent minimum of power consumption in the case of threshold value.
Although being described in conjunction with the accompanying embodiments of the present invention, those skilled in the art can not depart from this hair Various modifications and variations are made in the case of bright spirit and scope, such modifications and variations are each fallen within by appended claims Within limited range.

Claims (10)

  1. A kind of 1. control method of electrical conductivity in heavy metal wastewater thereby electrochemical treatment process, it is characterised in that including:
    S1, mass conservation law and Faraday's law based on Flow of Goods and Materials, establish the heavy metal ion molar concentration with time lag Mass balance model;
    S2, based on the heavy metal ion molar concentration mass balance model with time lag, establish at heavy metal wastewater thereby electrochemistry Power consumption Optimized model during reason so that power consumption in the case that concentration of heavy metal ion meets predetermined threshold value in outlet It is minimum;
    S3, the detection data of the entrance concentration of heavy metal ion of the electrolysis pending waste water of trough pool are obtained, it is excellent to the power consumption Change model adoption status branching algorithm and optimize solution, obtain so that exporting the feelings that concentration of heavy metal ion meets predetermined threshold value Best electrical conductivity numerical value under condition, so as to calculate Na needed for pretreatment process2SO4Addition.
  2. 2. the control method of electrical conductivity according to claim 1, it is characterised in that the heavy metal ion with time lag is rubbed You are specially at concentration mass balance model:
    <mrow> <mfrac> <mrow> <msub> <mi>dC</mi> <mi>A</mi> </msub> <mrow> <mo>(</mo> <mi>t</mi> <mo>)</mo> </mrow> </mrow> <mrow> <mi>d</mi> <mi>t</mi> </mrow> </mfrac> <mo>=</mo> <mfrac> <mi>f</mi> <mi>V</mi> </mfrac> <msubsup> <mi>C</mi> <mi>A</mi> <mrow> <mi>i</mi> <mi>n</mi> </mrow> </msubsup> <mrow> <mo>(</mo> <mi>t</mi> <mo>-</mo> <mi>&amp;tau;</mi> <mo>)</mo> </mrow> <mo>-</mo> <mfrac> <mi>f</mi> <mi>V</mi> </mfrac> <msub> <mi>C</mi> <mi>A</mi> </msub> <mrow> <mo>(</mo> <mi>t</mi> <mo>)</mo> </mrow> <mo>-</mo> <msub> <mi>r</mi> <mi>A</mi> </msub> </mrow>
    Wherein,It is the molar concentration rate of change of heavy metal ion A in electrolytic cell;It is heavy metal ion A entrance Molar concentration;τ is the time required to electrolyte flows to electrolytic cell from pretreatment process;CA(t) it is heavy metal ion A in electrolytic cell Molar concentration;F is the flow of entrance solution;V is the volume of electrolytic cell;rABe heavy metal ion A in electrolytic cell electrochemistry it is anti- Answer speed.
  3. 3. the control method of electrical conductivity according to claim 2, it is characterised in that heavy metal ion A in the electrolytic cell The kinetic model of electrochemical reaction speed be specially:
    <mrow> <msub> <mi>r</mi> <mi>A</mi> </msub> <mo>=</mo> <mfrac> <mrow> <mn>3</mn> <mi>S</mi> <mi>U</mi> <mi>&amp;kappa;</mi> <mo>&amp;lsqb;</mo> <mn>1</mn> <mo>-</mo> <mi>exp</mi> <mrow> <mo>(</mo> <mo>-</mo> <msub> <mi>&amp;beta;</mi> <mn>1</mn> </msub> <mi>t</mi> <mo>)</mo> </mrow> <mo>&amp;rsqb;</mo> </mrow> <mrow> <msub> <mi>&amp;beta;</mi> <mn>1</mn> </msub> <mi>t</mi> <mi>J</mi> <mi>z</mi> <mi>F</mi> <mo>&amp;lsqb;</mo> <mn>3</mn> <msub> <mi>L</mi> <mn>0</mn> </msub> <mi>S</mi> <mo>-</mo> <mn>4</mn> <msup> <mi>&amp;pi;R</mi> <mn>3</mn> </msup> <msub> <mi>VN</mi> <mi>A</mi> </msub> <mrow> <mo>(</mo> <msubsup> <mi>C</mi> <mi>A</mi> <mn>0</mn> </msubsup> <mo>-</mo> <msub> <mi>C</mi> <mi>A</mi> </msub> <mo>(</mo> <mi>t</mi> <mo>)</mo> </mrow> <mo>)</mo> <mo>&amp;rsqb;</mo> </mrow> </mfrac> </mrow>
    Wherein, S is polar plate area;U is decomposition voltage;κ is electrical conductivity;Z be electrode reaction transfer charge number, take on the occasion of;F is Faraday constant;L0For the initial spacing of pole plate;R is iron atom radius;V is the volume of electrolytic cell;NAIt is that Avogadro is normal Number;It is the initial molar concentration of A ions;β1It is parameter to be identified;J is electrolytic current density.
  4. 4. the control method of electrical conductivity according to claim 1, it is characterised in that the power consumption Optimized model is specific For:
    <mrow> <mi>m</mi> <mi>i</mi> <mi>n</mi> <mrow> <mo>(</mo> <mi>W</mi> <mo>)</mo> </mrow> <mo>=</mo> <mi>m</mi> <mi>i</mi> <mi>n</mi> <msubsup> <mo>&amp;Integral;</mo> <msub> <mi>t</mi> <mn>0</mn> </msub> <msub> <mi>t</mi> <mi>f</mi> </msub> </msubsup> <mrow> <mo>(</mo> <mi>m</mi> <mo>&amp;times;</mo> <mi>S</mi> <mo>&amp;times;</mo> <mi>U</mi> <mo>&amp;times;</mo> <mi>J</mi> <mo>)</mo> </mrow> <mi>d</mi> <mi>t</mi> </mrow>
    <mrow> <mi>s</mi> <mo>.</mo> <mi>t</mi> <mfenced open = "{" close = ""> <mtable> <mtr> <mtd> <msub> <mover> <mi>C</mi> <mo>&amp;CenterDot;</mo> </mover> <mi>A</mi> </msub> <mo>(</mo> <mi>t</mi> <mo>)</mo> <mo>=</mo> <mfrac> <mi>f</mi> <mi>V</mi> </mfrac> <msubsup> <mi>C</mi> <mi>A</mi> <mrow> <mi>i</mi> <mi>n</mi> </mrow> </msubsup> <mo>(</mo> <mi>t</mi> <mo>-</mo> <mi>&amp;tau;</mi> <mo>)</mo> <mo>-</mo> <mfrac> <mi>f</mi> <mi>V</mi> </mfrac> <msub> <mi>C</mi> <mi>A</mi> </msub> <mo>(</mo> <mi>t</mi> <mo>)</mo> <mo>-</mo> <msub> <mi>r</mi> <mi>A</mi> </msub> </mtd> </mtr> <mtr> <mtd> <mrow> <mi>U</mi> <mo>=</mo> <mi>g</mi> <mrow> <mo>(</mo> <msub> <mi>C</mi> <mi>A</mi> </msub> <mo>,</mo> <mi>J</mi> <mo>,</mo> <mi>L</mi> <mo>,</mo> <mi>&amp;kappa;</mi> <mo>)</mo> </mrow> </mrow> </mtd> </mtr> <mtr> <mtd> <msubsup> <mi>C</mi> <mi>A</mi> <mrow> <mi>o</mi> <mi>u</mi> <mi>t</mi> </mrow> </msubsup> <mo>&amp;le;</mo> <msubsup> <mi>C</mi> <mi>A</mi> <mi>max</mi> </msubsup> </mtd> </mtr> <mtr> <mtd> <mrow> <mi>U</mi> <mo>&amp;le;</mo> <msub> <mi>U</mi> <mrow> <mi>m</mi> <mi>a</mi> <mi>x</mi> </mrow> </msub> </mrow> </mtd> </mtr> </mtable> </mfenced> </mrow>
    Wherein, W is power consumption;M is minus plate number;S is every piece of minus plate area;U is tank voltage;t0And tfRespectively it is electrolysed Start the time with terminating;It is outlet heavy metal ion A concentration;J is current density;κ is that electrical conductivity L is pole plate spacing;It is the desired value that wastewater outlet heavy metal ion A concentration should reach;UmaxThe upper voltage limit that can bear for battery lead plate.
  5. 5. the control method of electrical conductivity according to claim 4, it is characterised in that in the power consumption Optimized model Tank voltage U and concentration of heavy metal ion CA, the relation between current density, J be specially:
    Wherein,It is the equilibrium potential constant of A elemental releases;V is the volume of electrolytic cell;S is polar plate area;R is that thermodynamics is normal Number;F is Faraday constant;It is the initial molar concentration of A ions;L0For the initial spacing of pole plate;T is electrolysis temperature;R is A The activity coefficient of ion;MAIt is heavy metal A relative atomic weight;α15For parameter to be identified.
  6. 6. the control method of electrical conductivity according to claim 1, it is characterised in that calculated in the S3 in pretreatment process Required Na2SO4Addition concretely comprise the following steps:
    S31, the molar conductivity of solution can be obtained according to Cole Lao Wushi empirical equations, and be calculated when electrical conductivity is κ When Na2SO4Molar concentration:
    <mrow> <msub> <mi>&amp;Lambda;</mi> <mi>&amp;alpha;</mi> </msub> <mo>=</mo> <msubsup> <mi>&amp;Lambda;</mi> <mi>&amp;alpha;</mi> <mn>0</mn> </msubsup> <mo>-</mo> <mi>&amp;beta;</mi> <msqrt> <msub> <mi>C</mi> <mi>&amp;alpha;</mi> </msub> </msqrt> </mrow>
    Wherein, ΛαFor Na2SO4The molar conductivity of solution, the relation with electrical conductivity κ are Λα=κ/Cα;CαFor Na2SO4Mole Concentration;For Na2SO4The limiting molar conductivity of solution;β is constant;
    S32, according to the Na2SO4Molar concentration, calculate required Na2SO4Addition, calculation formula is specially:
    mα=CαMαV
    Wherein, mαFor required Na2SO4Addition quality;MαFor Na2SO4Molal weight;V is electrolytic cell volume.
  7. A kind of 7. control device of electrical conductivity in heavy metal wastewater thereby electrochemical treatment process, it is characterised in that including:
    First model establishes unit, for mass conservation law and Faraday's law based on Flow of Goods and Materials, establishes with time lag Heavy metal ion molar concentration mass balance model;
    Second model establishes unit, for based on the heavy metal ion molar concentration mass balance model with time lag, establishing Power consumption Optimized model in heavy metal wastewater thereby electrochemical treatment process so that concentration of heavy metal ion meets default threshold in outlet Power consumption is minimum in the case of value;
    Control unit, the detection data of the entrance concentration of heavy metal ion for obtaining the electrolysis pending waste water of trough pool, to described Power consumption Optimized model adoption status branching algorithm optimizes solution, obtains meeting in advance so that exporting concentration of heavy metal ion If the best electrical conductivity numerical value in the case of threshold value, so as to calculate Na needed for pretreatment process2SO4Addition.
  8. 8. the control device of electrical conductivity according to claim 7, it is characterised in that including:
    First computing unit, for the molar conductivity of solution can be obtained according to Cole Lao Wushi empirical equations, and calculate To the Na when electrical conductivity is κ2SO4Molar concentration:
    <mrow> <msub> <mi>&amp;Lambda;</mi> <mi>&amp;alpha;</mi> </msub> <mo>=</mo> <msubsup> <mi>&amp;Lambda;</mi> <mi>&amp;alpha;</mi> <mn>0</mn> </msubsup> <mo>-</mo> <mi>&amp;beta;</mi> <msqrt> <msub> <mi>C</mi> <mi>&amp;alpha;</mi> </msub> </msqrt> </mrow>
    Wherein, ΛαFor Na2SO4The molar conductivity of solution, the relation with electrical conductivity κ are Λα=κ/Cα;CαFor Na2SO4Mole Concentration;For Na2SO4The limiting molar conductivity of solution, is typically obtained by extrapolation;β is constant;
    Second computing unit, for according to the Na2SO4Molar concentration, calculate required Na2SO4Addition, calculation formula Specially:
    mα=CαMαV
    Wherein, mαFor required Na2SO4Addition quality;MαFor Na2SO4Molal weight;V is electrolytic cell volume.
  9. 9. the control device of electrical conductivity according to claim 7, it is characterised in that first model establishes unit foundation The heavy metal ion molar concentration mass balance model with time lag be specially:
    <mrow> <mfrac> <mrow> <msub> <mi>dC</mi> <mi>A</mi> </msub> <mrow> <mo>(</mo> <mi>t</mi> <mo>)</mo> </mrow> </mrow> <mrow> <mi>d</mi> <mi>t</mi> </mrow> </mfrac> <mo>=</mo> <mfrac> <mi>f</mi> <mi>V</mi> </mfrac> <msubsup> <mi>C</mi> <mi>A</mi> <mrow> <mi>i</mi> <mi>n</mi> </mrow> </msubsup> <mrow> <mo>(</mo> <mi>t</mi> <mo>-</mo> <mi>&amp;tau;</mi> <mo>)</mo> </mrow> <mo>-</mo> <mfrac> <mi>f</mi> <mi>V</mi> </mfrac> <msub> <mi>C</mi> <mi>A</mi> </msub> <mrow> <mo>(</mo> <mi>t</mi> <mo>)</mo> </mrow> <mo>-</mo> <msub> <mi>r</mi> <mi>A</mi> </msub> </mrow>
    Wherein,It is the molar concentration rate of change of heavy metal ion A in electrolytic cell;It is heavy metal ion A entrance Molar concentration;τ is the time required to electrolyte flows to electrolytic cell from pretreatment process;CA(t) it is heavy metal ion A in electrolytic cell Molar concentration;F is the flow of entrance solution;V is the volume of electrolytic cell;rABe heavy metal ion A in electrolytic cell electrochemistry it is anti- Answer speed.
  10. 10. the control device of electrical conductivity according to claim 7, it is characterised in that second model is established unit and built Vertical power consumption Optimized model is specially:
    <mrow> <mi>m</mi> <mi>i</mi> <mi>n</mi> <mrow> <mo>(</mo> <mi>W</mi> <mo>)</mo> </mrow> <mo>=</mo> <mi>m</mi> <mi>i</mi> <mi>n</mi> <msubsup> <mo>&amp;Integral;</mo> <msub> <mi>t</mi> <mn>0</mn> </msub> <msub> <mi>t</mi> <mi>f</mi> </msub> </msubsup> <mrow> <mo>(</mo> <mi>m</mi> <mo>&amp;times;</mo> <mi>S</mi> <mo>&amp;times;</mo> <mi>U</mi> <mo>&amp;times;</mo> <mi>J</mi> <mo>)</mo> </mrow> <mi>d</mi> <mi>t</mi> </mrow>
    <mrow> <mi>s</mi> <mo>.</mo> <mi>t</mi> <mfenced open = "{" close = ""> <mtable> <mtr> <mtd> <msub> <mover> <mi>C</mi> <mo>&amp;CenterDot;</mo> </mover> <mi>A</mi> </msub> <mo>(</mo> <mi>t</mi> <mo>)</mo> <mo>=</mo> <mfrac> <mi>f</mi> <mi>V</mi> </mfrac> <msubsup> <mi>C</mi> <mi>A</mi> <mrow> <mi>i</mi> <mi>n</mi> </mrow> </msubsup> <mo>(</mo> <mi>t</mi> <mo>-</mo> <mi>&amp;tau;</mi> <mo>)</mo> <mo>-</mo> <mfrac> <mi>f</mi> <mi>V</mi> </mfrac> <msub> <mi>C</mi> <mi>A</mi> </msub> <mo>(</mo> <mi>t</mi> <mo>)</mo> <mo>-</mo> <msub> <mi>r</mi> <mi>A</mi> </msub> </mtd> </mtr> <mtr> <mtd> <mrow> <mi>U</mi> <mo>=</mo> <mi>g</mi> <mrow> <mo>(</mo> <msub> <mi>C</mi> <mi>A</mi> </msub> <mo>,</mo> <mi>J</mi> <mo>,</mo> <mi>L</mi> <mo>,</mo> <mi>&amp;kappa;</mi> <mo>)</mo> </mrow> </mrow> </mtd> </mtr> <mtr> <mtd> <msubsup> <mi>C</mi> <mi>A</mi> <mrow> <mi>o</mi> <mi>u</mi> <mi>t</mi> </mrow> </msubsup> <mo>&amp;le;</mo> <msubsup> <mi>C</mi> <mi>A</mi> <mi>max</mi> </msubsup> </mtd> </mtr> <mtr> <mtd> <mrow> <mi>U</mi> <mo>&amp;le;</mo> <msub> <mi>U</mi> <mrow> <mi>m</mi> <mi>a</mi> <mi>x</mi> </mrow> </msub> </mrow> </mtd> </mtr> </mtable> </mfenced> </mrow>
    Wherein, W is power consumption;M is minus plate number;S is every piece of minus plate area;U is tank voltage;t0And tfRespectively it is electrolysed Start the time with terminating;It is outlet heavy metal ion A concentration;J is current density;κ is electrical conductivity;L is pole plate spacing;It is the desired value that wastewater outlet heavy metal ion A concentration should reach;UmaxThe upper voltage limit that can bear for battery lead plate.
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