CN109033614A - Method based on electrode reaction prediction valve cooling system screening electrodes dirt thickness degree - Google Patents
Method based on electrode reaction prediction valve cooling system screening electrodes dirt thickness degree Download PDFInfo
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Abstract
The invention discloses a kind of methods based on electrode reaction prediction converter valve screening electrodes dirt thickness degree.To solve electrochemical corrosion and problems of excessive heat caused by screening electrodes fouling in current converter valve water-cooling system, the technical solution adopted by the present invention are as follows: for the cooling converter valve section inner cold system structure in parallel connection water route used by certain converter station, determine the physical model structure of valve section water route electrode reaction, and according to operating condition, and then establish the computation model of valve section water route electrode reaction;The initial value and boundary condition of operating voltage value setting electrode potential and deionized water current potential when being run using water route geometric parameter, quality of de-ionized water parameter and converter valve;Construct electrode reaction model;Solve electrode fouling thickness.The present invention is conducive to further obtain the fouling data of screening electrodes in converter valve operational process, grasps electrode scaling rule, in time replacement converter valve screening electrodes, supports to ensure that converter station safe and stable operation provides strong theory and technology.
Description
Technical field
The present invention relates to the cooling systems of equipment in HVDC transmission system, especially a kind of anti-based on non linear electrodes
The method that should predict valve cooling system screening electrodes dirt thickness degree.
Background technique
Converter valve is the key equipment of HVDC transmission system, and valve cooling system is the weak spot of converter valve, is more than
25% converter valve failure is caused by valve cooling system.Converter valve can generate amount of heat in the course of work, and valve cooling system passes through
Recirculated cooling water takes away heat, so that converter valve works normally.Since metal component current potential each in converter valve is different, cooling water with
Metal component directly contacts, and Leakage Current can be generated between metalwork, cause the corrosion of metal component.By installing equal piezoelectricity
Pole reveals electric current at screening electrodes, to avoid generating Leakage Current between metal component, but therefore screening electrodes also exist
Continuous fouling in operational process.After electrode fouling is serious, it will lead to dirty layer and fall off, further cause cooling water pipe blocking and the change of current
Stand stoppage in transit the problem of.
The domestic method for solving screening electrodes fouling is periodic inspection cleaning at present, but still will appear dirt using the method
The case where layer falls off, and cooling water pipe blocking, converter station is caused to be stopped transport, and the method needs converter station of stopping transport, and causes certain warp
Ji loss, it is also necessary to put into biggish manpower and material resources.
Therefore, further go deep into is needed to the computational problem of converter valve inner cold system water route electrode reaction and dirty thickness degree
Research to grasp electrode scaling rule, and then improves electrode fouling condition.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the problems of the above-mentioned prior art, provide a kind of based on non-thread
Property electrode reaction prediction valve cooling system screening electrodes dirt thickness degree method, pass through the numerical simulation to electrode reaction, realize
The calculating of electrode dirt thickness degree under different operating conditions, for further obtain converter valve operational process in screening electrodes fouling data,
Replacement converter valve screening electrodes, guarantee converter station safe and stable operation provide strong theory and technology and support in time.
To achieve the above object, the present invention adopts the following technical scheme: predicting the equal piezoelectricity of valve cooling system based on electrode reaction
The method of extremely dirty thickness degree comprising following steps:
Step 1 is determined for the cooling converter valve section inner cold system structure in parallel connection water route used by certain converter station
The physical model structure of valve section water route electrode reaction, and according to operating condition, and then establish the calculating of valve section water route electrode reaction
Model;
Step 2, operating voltage value is set when being run using water route geometric parameter, quality of de-ionized water parameter and converter valve
Set the initial value and boundary condition of electrode potential and deionized water current potential;
Step 3 hinders shadow in conjunction with deionized water flow field and concentration field characteristic, electrode kinetics boundary condition, electrode dirt tunic
It rings, the nonlinear characteristic of electric double layer capacitance, constructs electrode reaction model;
Step 4, the Faraday's law based on deposition Yu kinetic current density relationship solve electrode fouling thickness;
Step 5, according to above-mentioned steps, numerical value calculates different voltages grade, different deionized water flow velocitys, difference [Al respectively
(OH)4]-Water route electrode reaction under ion concentration, and solve and calculate electrode fouling thickness.
As the supplement of the above method, in step 1, the physical model structure of the valve section water route electrode reaction includes:
Two platinum electrodes, water pipe and deionized water with water swivel, deionized water is led in the water pipe, and two platinum electrodes are mounted on
On water pipe;The valve section water route electrode reaction are as follows:
Anode: 4 [Al (OH)4]--4e-→2Al2O3↓+8H2O+O2↑,
Cathode: O2+2H2O+4e-→4OH-。
As the supplement of the above method, in step 2, the water route geometric parameter includes: the length of water pipe, diameter, electricity
The installation site of pole, the length of electrode and insertion water pipe depth.
As the supplement of the above method, in step 2, the quality of de-ionized water parameter includes: deionized water conductance
Rate, [Al (OH)4]-The concentration of ion.
As the supplement of the above method, in step 2, the initial value and side of the electrode potential and deionized water current potential
The concrete condition of boundary's condition are as follows:
1) initial value
Based on finite element method, to solve convergence, anode potential is set as the potential value of anode surface boundary condition;
Cathode electrode ground connection, deionized water current potential are the negative value that cathode electrode reacts equilibrium potential, it may be assumed that
Indicate electrode potential;Indicate deionized water current potential;Indicate that cathode electrode reacts equilibrium potential;
2) boundary condition
Consider that screening electrodes are connect with radiator, and radiator is close to thyristor, thus the voltage waveform on electrode with change
Voltage waveform when flowing valve operation is consistent, so using half-wave sinusoidal voltage;
Anode surface:Cathode surface:
As the supplement of the above method, in step 3, the electrode kinetics boundary condition are as follows: using characterization overpotential
It writes from memory equation with Butler-Wall of kinetic current relationship:
In formula, ilocRefer to local reaction current density, A/m2;ioRefer to exchange current density, A/m2;αaIt is exchanged for anode and is
Number, αcFor cathode exchange coefficient, F is Faraday constant, C/mol;η is overpotential, V;R is gas constant, J/ (Kmol);T
For thermodynamic temperature, K;
Anode Tafel equation are as follows:
In formula, AcFor Tafel slope;η is overpotential, V;ioRefer to exchange current density, A/m2, wherein anode electrode reacts
With the silent equation characterization in Butler-Wall, cathode electrode reaction is characterized since overpotential η is small using anode Tafel equation;
Consider the activation polarization of electrode process, overpotential
In formula, Eeq indicates the equilibrium potential of electrode reaction, V;Indicate electrode potential;Indicate deionized water current potential.
As the supplement of the above method, in step 3, the electrode dirt tunic, which hinders, to be influenced, and is specifically described are as follows:
1) electrode dirt layer conductivityσ is setfilm;
2) dirty layer original depth S is set0;
3) the dynamic change dirt layer thickness deltat S of electrode reaction is calculated;
Establish the dynamic surface resistance of electrode and electrolyte interface
As the supplement of the above method, in step 3, the nonlinear characteristic of the electric double layer capacitance is specifically described
Are as follows:
Since the thickness of electrode and the electric double layer of bath surface formation is much smaller than electrode curvature, electric double layer is considered as
Capacity plate antenna, but its unit area equivalent capacity CdMeet the non-linear relation of following formula with its both end voltage u:
In formula, CdTo disperse layer capacitance, F/m2, z expression ionic charge number;E indicates electronic charge, C;εrIndicate opposite
Dielectric constant;ε0Indicate permittivity of vacuum, F/m;K indicates Boltzmann constant, J/K;T indicates thermodynamic temperature, K;n0=C*
NA, indicate Particle density of the ion in bulk solution, L-1;C*Indicate electrolyte aqueous solution concentration, mol/L;NAIndicate Avobenzene gal moral
Sieve constant.
It is described that dirty layer is asked based on deposition and kinetic current density relationship in step 4 as the supplement of the above method
Thickness is described in detail below:
The kinetic current i of anode surface is acquired by the silent equation in Butler-Wall firstloc, according to Faraday's law: occurring
The amount of substance of cell reaction is directly proportional to the electricity passed through, calculates Al by following formula2O3Deposition,
In formula, n indicates the amount of product substance, mol;Q indicates the electricity by electrode surface, C;I indicates electrode current,
A;T indicates time, s;Z indicates charge number, C;F indicates Faraday constant, C/mol.
As the supplement of the above method, in step 5, the different voltages grade is: 25-100Kv;Different deionizations
Water flow velocity is: 1-6m/s;Ion concentration range is: 1*10-5-1*10-6mol/m3。
The present invention is primarily based on converter valve water-cooling system screening electrodes dirt layer element and sedimentation mechanism, and meter and electrode reaction
Electric double layer capacitance effect, and using Butler-Wall write from memory equation overpotential and electrode reaction current density relationship are described, into
And construct the electrode reaction nonlinear model considered under the effect of screening electrodes non sinusoidal periodic voltage;Secondly, considering electrode insulation
Characteristic and its dynamic growth process and neighbouring electrolyte potential influence, and the screening electrodes constructed under high field, turbulent flow are non-thread
Property model, in a model by establishing the dynamic surface resistance of coupling electrode dirt thickness degree in electrode and electrolyte interface, with
Cause after reflection electrode dynamic scale formation electrode nearby electric field distortion the case where, according to the relationship of kinetic current density and deposition,
Electrode fouling thickness distribution is solved, realizes the dirty layer thickness prediction of non linear electrodes reaction.
The present invention is conducive to further obtain the fouling data of screening electrodes in converter valve operational process, grasps electrode fouling
Rule, in time replacement converter valve screening electrodes are supported to ensure that converter station safe and stable operation provides strong theory and technology.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention, for those of ordinary skill in the art, without any creative labor, according to
These attached drawings obtain other attached drawings and still fall within scope of the invention
Fig. 1 is the flow chart that the method for valve cooling system screening electrodes dirt thickness degree is predicted the present invention is based on electrode reaction;
Fig. 2 is the structural schematic diagram of the physical model of valve section water route electrode reaction in the embodiment of the present invention.
Specific embodiment
It is understandable to be more clear the purpose of the present invention, feature, step, advantage, in the following with reference to the drawings and specific embodiments
The present invention is described in detail.Firstly the need of explanation, the present invention is not limited to following specific embodiments, this field
The spirit that technical staff should be embodied from following embodiments understands the present invention, and each technical term can be based on of the invention
Spirit Essence does broadest understanding.
Embodiment 1
The present embodiment provides a kind of method based on electrode reaction prediction valve cooling system screening electrodes dirt thickness degree, such as Fig. 1
It is shown, comprising the following steps:
Step 1: the converter valve section inner cold system structure for using water route in parallel cooling for certain converter station determines valve
The physical model structure of Duan Shuilu electrode reaction, and according to operating condition, and then establish the calculating mould of valve section water route electrode reaction
Type;
Step 2: operating voltage value is set when being run using water route geometric parameter, quality of de-ionized water parameter and converter valve
Set the initial value and boundary condition of electric electrode potential and deionized water current potential;
Step 3: shadow is hindered in conjunction with deionized water flow field and concentration field characteristic, electrode kinetics boundary condition, electrode dirt tunic
It rings, the nonlinear characteristic of electric double layer capacitance, constructs electrode reaction model;Electrode when based on faraday's principle solving electrode reaction
Fouling thickness;
Step 4: according to above-mentioned steps, difference numerical simulation different voltages grade, different deionized water flow velocitys, difference [Al
(OH)4]-Water route electrode reaction under ion concentration, and solve and calculate electrode fouling thickness.
The physical model structure of valve section water route electrode reaction is as shown in Fig. 2, include two platinum electrodes, the water with water swivel
Pipe, deionized water.
Valve section water route electrode reaction in step 1 are as follows:
Anode: 4 [Al (OH)4]--4e-→4Al2O3↓+2H2O3+O2↑,
Cathode: O2+2H2O+4e-→4OH-。
In step 2, the concrete condition of the initial value and boundary condition of electrode potential and deionized water current potential are as follows:
1) initial value
Based on finite element method, to solve convergence, anode potential is set as the potential value of anode surface boundary condition;
Cathode electrode ground connection, deionized water current potential are the negative value that cathode electrode reacts equilibrium potential, it may be assumed that
2) boundary condition
Consider that screening electrodes are connect with radiator, and radiator is close to thyristor, thus the voltage waveform on electrode with change
Voltage waveform when flowing valve operation is consistent, so using half-wave sinusoidal voltage.
Anode surface:Cathode surface:
Step 3, the electrode kinetics boundary condition are as follows: using the Bart of characterization overpotential and kinetic current relationship
It writes from memory equation Le-Wall:
In formula, ilocRefer to local reaction current density, A/m2;ioRefer to exchange current density, A/m2;αaIt is exchanged for anode and is
Number, αcFor cathode exchange coefficient, F is Faraday constant, C/mol;η is overpotential, V;R is gas constant, J/ (Kmol);T
For thermodynamic temperature, K.
Anode Tafel equation are as follows:
In formula, AcFor Tafel slope;η is overpotential, V;ioRefer to exchange current density, A/m2.Wherein anode electrode reacts
With the silent equation characterization in Butler-Wall, cathode electrode reaction is characterized since overpotential η is small using anode Tafel equation.
Consider the activation polarization of electrode process, overpotential
Step 3, the consideration electrode dirt tunic, which hinders, to be influenced, and is specifically described are as follows:
1) electrode dirt layer conductivityσ is setfilm;
2) dirty layer original depth S0 is set;
3) the dynamic change dirt layer thickness deltat S of electrode reaction is calculated;
Establish the dynamic surface resistance of electrode and electrolyte interface
Step 3, the nonlinear characteristic of the consideration electric double layer capacitance, specifically describes are as follows:
Since the thickness of electrode and the electric double layer of bath surface formation is much smaller than electrode curvature, electric double layer is considered as
Capacity plate antenna, but its unit area equivalent capacity CdMeet the non-linear relation of following formula with its both end voltage u:
CdTo disperse layer capacitance, F/m2, z expression ionic charge number;E indicates electronic charge, C;εrIndicate that opposite dielectric is normal
Number;ε0Indicate permittivity of vacuum, F/m;K indicates Boltzmann constant, J/K;T indicates thermodynamic temperature, K;n0=C*NA, table
Show Particle density of the ion in bulk solution, L-1;C*Indicate electrolyte aqueous solution concentration, mol/L;NAIndicate that Avogadro is normal
Number.
Step 3, the dirty thickness degree that electrode reaction is solved based on Faraday's law are described in detail below: first
The kinetic current i of anode surface can be acquired by the silent equation in Butler-Wallloc, Al can be calculated according to the following formula2O3Deposition.
In formula, n indicates the amount of product substance, mol;Q indicates the electricity by electrode surface, C;I indicates electrode current,
A;T indicates time, s;Z indicates charge number, C;F indicates Faraday constant, C/mol.
The water route geometric parameter includes: the length of water pipe, diameter, the installation position of electrode, the length of electrode and is inserted
Water inlet pipe depth;The quality of de-ionized water parameter includes: deionized water conductivity, [Al (OH)4]-The concentration of ion.
For a person skilled in the art, after reading above description, various changes and modifications undoubtedly be will be evident.
Therefore, appended claims should regard the whole variations and modifications for covering true intention and range of the invention as.It is weighing
The range and content of any and all equivalences, are all considered as still belonging to the intent and scope of the invention within the scope of sharp claim.
Claims (9)
1. the method based on electrode reaction prediction valve cooling system screening electrodes dirt thickness degree, which comprises the following steps:
Step 1 determines valve section for the cooling converter valve section inner cold system structure in parallel connection water route used by certain converter station
The physical model structure of water route electrode reaction, and according to operating condition, and then establish the computation model of valve section water route electrode reaction;
Step 2, electricity is arranged in operating voltage value when being run using water route geometric parameter, quality of de-ionized water parameter and converter valve
The initial value and boundary condition of electrode potential and deionized water current potential;
Step 3, influenced in conjunction with deionized water flow field and concentration field characteristic, electrode kinetics boundary condition, the resistance of electrode dirt tunic,
The nonlinear characteristic of electric double layer capacitance constructs electrode reaction model;
Step 4, the Faraday's law based on deposition Yu kinetic current density relationship solve electrode fouling thickness;
Step 5, according to above-mentioned steps, numerical value calculates different voltages grade, different deionized water flow velocitys, difference [Al respectively
(OH)4]-Water route electrode reaction under ion concentration, and solve and calculate electrode fouling thickness.
2. the method according to claim 1 based on electrode reaction prediction valve cooling system screening electrodes dirt thickness degree, special
Sign is, in step 1, the physical model structure of the valve section water route electrode reaction includes: two platinum electrodes, connects with water
The water pipe and deionized water of head, deionized water is led in the water pipe, and two platinum electrodes are mounted on water pipe;The valve Duan Shui
Path electrode reaction are as follows:
Anode: 4 [Al (OH)4]--4e-→2Al2O3↓+8H2O+O2↑,
Cathode: O2+2H2O+4e-→4OH-。
3. the method according to claim 1 based on electrode reaction prediction valve cooling system screening electrodes dirt thickness degree, special
Sign is, in step 2, the water route geometric parameter includes: the length of water pipe, diameter, the installation site of electrode, electrode
Length and insertion water pipe depth.
4. the method according to claim 1 based on electrode reaction prediction valve cooling system screening electrodes dirt thickness degree, special
Sign is, in step 2, the quality of de-ionized water parameter includes: deionized water conductivity, [Al (OH)4]-Ion it is dense
Degree.
5. the method according to claim 1 based on electrode reaction prediction valve cooling system screening electrodes dirt thickness degree, special
Sign is, in step 2, the concrete condition of the initial value and boundary condition of the electrode potential and deionized water current potential are as follows:
1) initial value
Based on finite element method, to solve convergence, anode potential is set as the potential value of anode surface boundary condition;Cathode
Electrode ground connection, deionized water current potential are the negative value that cathode electrode reacts equilibrium potential, it may be assumed that
Indicate electrode potential;Indicate deionized water current potential;Indicate that cathode electrode reacts equilibrium potential;
2) boundary condition
Consider that screening electrodes are connect with radiator, and radiator is close to thyristor, therefore voltage waveform and converter valve on electrode
Voltage waveform when operation is consistent, so using half-wave sinusoidal voltage;
Anode surface:
Cathode surface:
6. the method according to claim 1 based on electrode reaction prediction valve cooling system screening electrodes dirt thickness degree, special
Sign is, in step 3, the electrode kinetics boundary condition are as follows: using the Bart of characterization overpotential and kinetic current relationship
It writes from memory equation Le-Wall:
In formula, ilocRefer to local reaction current density, A/m2;ioRefer to exchange current density, A/m2;αaFor anode exchange coefficient, αcFor
Cathode exchange coefficient, F are Faraday constant, C/mol;η is overpotential, V;R is gas constant, J/ (Kmol);T is thermodynamics
Temperature, K;
Anode Tafel equation are as follows:
In formula, AcFor Tafel slope;η is overpotential, V;ioRefer to exchange current density, A/m2, wherein anode electrode reacts use bar
The silent equation characterization in Teller-Wall, cathode electrode reaction are characterized since overpotential η is small using anode Tafel equation;
Consider the activation polarization of electrode process, overpotential
In formula, Eeq indicates the equilibrium potential of electrode reaction, V;Indicate electrode potential;Indicate deionized water current potential.
7. the method according to claim 1 based on electrode reaction prediction valve cooling system screening electrodes dirt thickness degree, special
Sign is, in step 3, the electrode dirt tunic, which hinders, to be influenced, and specifically describes are as follows:
1) electrode dirt layer conductivityσ is setfilm;
2) dirty layer original depth S is set0;
3) the dynamic change dirt layer thickness deltat S of electrode reaction is calculated;
Establish the dynamic surface resistance of electrode and electrolyte interface
8. the method according to claim 1 based on electrode reaction prediction valve cooling system screening electrodes dirt thickness degree, special
Sign is, in step 3, the nonlinear characteristic of the electric double layer capacitance is specifically described are as follows:
Since the thickness of electrode and the electric double layer of bath surface formation is much smaller than electrode curvature, electric double layer is considered as plate
Capacitor, but its unit area equivalent capacity CdMeet the non-linear relation of following formula with its both end voltage u:
In formula, CdTo disperse layer capacitance, F/m2, z expression ionic charge number;E indicates electronic charge, C;εrIndicate opposite dielectric
Constant;ε0Indicate permittivity of vacuum, F/m;K indicates Boltzmann constant, J/K;T indicates thermodynamic temperature, K;n0=C*NA,
Indicate Particle density of the ion in bulk solution, L-1;C*Indicate electrolyte aqueous solution concentration, mol/L;NAIndicate Avogadro
Constant.
9. the method according to claim 1 based on electrode reaction prediction valve cooling system screening electrodes dirt thickness degree, special
Sign is, described to ask being described in detail below for dirty thickness degree based on deposition and kinetic current density relationship in step 4:
The kinetic current i of anode surface is acquired by the silent equation in Butler-Wall firstloc, according to Faraday's law: being electrolysed
The amount of substance of reaction is directly proportional to the electricity passed through, calculates Al by following formula2O3Deposition,
In formula, n indicates the amount of product substance, mol;Q indicates the electricity by electrode surface, C;I indicates electrode current, A;t
Indicate time, s;Z indicates charge number, C;F indicates Faraday constant, C/mol.
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