CN106503462B - Dynamic current in electrocatalytic oxidation regulates and controls method - Google Patents
Dynamic current in electrocatalytic oxidation regulates and controls method Download PDFInfo
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Abstract
The present invention discloses a kind of dynamic current regulation method in electrocatalytic oxidation, comprising: 1) according to the electro-catalysis system of actual motion calculate it corresponding to mass tranfer coefficient km；2) during reacting progress, the actual value of the COD or TOC of solution are detected；3) limiting current density value j corresponding to COD the or TOC value of etching solution at this time is calculatedlim；4) gained limiting current density value j is calculated according to step 3)lim, corresponding current value is obtained in conjunction with the annode area of electro-catalysis system used, and this moment or the current value of subsequent time with this current value adjustment electro-catalysis system.Dynamic current adjustment of the present invention, runs so that the electrocatalytic oxidation process of organic matter is in always in the state that actual current density is equal or slightly larger than limiting current density.It can effectively ensure that electro-catalysis system is run during whole service with the current efficiency equal or close to 100% in this way, great energy saving, while can guarantee the effect of processing.
Description
Technical field
The invention belongs to electrochemical technology field, in particular to a kind of dynamic current tune for during electrocatalytic oxidation
Prosecutor method.
Background technique
It is typical high-level oxidation technology that electrocatalytic oxidation, which handles organic matter technology, in recent years by more scientific research personnel's
Pay close attention to (Applied Catalysis B:Environmental, 2009,87,105-145；Chemical Society
reviews,2006,35,1324-1340；Chem.Rev.,2009,109,6541-6569).Influence electro-catalytic oxidation technology
There are many factor, and different factors can generate large effect, such as current density value, organic concentration, solution temperature to final result
Degree, solution ph etc..Research emphasis in recent years is also next around improving its treatment effect, treatment effeciency and reducing processing energy consumption
It carries out.
In the influence factor of aforementioned electro-catalysis process, current density be influence Electrocatalysis Degradation process current efficiency and
The important indicator of power consumption values.Current research report is all to investigate current density value size for treatment process and treatment effect
It influences, yet there are no influence research report of the electric current presentation mode for processing.
Common powering mode includes constant pressure powering mode, constant current power mode and pulse power supply during electrocatalytic oxidation
Mode.
Constant pressure powering mode be constant voltage is provided during electrocatalytic oxidation, and electric current can with cell reaction into
There is different variations (can constantly become smaller in general) in row.Equipment needed for this powering mode is fairly simple；But text at present
It offers in data and engineering practice, the seldom of Electrocatalysis Degradation is carried out using this mode, be primarily due to constant voltage mode and calculating respectively
It is comparatively laborious when kind in-process metrics (especially current efficiency).At the same time, since electric current in constant voltage process can be over time
And constantly reduce, show that its provided reaction motive force also constantly reduces, and is unfavorable for the lasting progress of electrocatalytic oxidation process.
Constant current power mode is that constant electric current is provided in electrolytic process, and voltage with cell reaction can occur
Different variations (can be continuously increased in general).Equipment needed for this powering mode is relative complex.At present documents and materials and
In engineering practice, most Electrocatalysis Degradations is carried out using such mode.Main reason is that: (1) mode it is simple,
Equipment is cheap, is easily manipulated and automates；(2) convenient and simple when calculating various processes index.
Pulse power supply mode is that the electric current of a pulsed is provided in electrolytic process, and voltage can be with the concrete condition of pulse
And different variations occurs.This powering mode is complicated, needs special instrument and equipment guarantee.Document report and engineering at present
In practice, it yet there are no researcher's strobe pulse powering mode and go to implement the electrocatalytic oxidation of organic matter.
Documents and materials (Chemosphere, 2010,81,26-32；Electrochimica Acta,2015,154,278-
286；Chemical Engineering Journal, 2014,245,359-366) show the organic matter to various concentration into
When row Electro-catalytic Oxidation Process, there are a specific limiting current density value (jlim), shown in basic relational expression such as formula (1).
jlim=4FkmCOD0 (1)
In formula (1), jlimFor limiting current density value, unit Am–2；F is Faraday constant, value 96487C
mol–1；kmFor mass tranfer coefficient, unit ms–1；COD0For the initial COD value of solution, unit mgL-1.By COD value in formula (1)
When being substituted for TOC value, corresponding jlimWith kmThen become corresponding numerical value under the conditions of TOC respectively.
When actual current density is in jlimUnder when, the number of electrons for indicating that electro-catalysis system provides cannot will be handled
Organic molecule complete oxidation (utilizing COD COD calculating current efficiency) or mineralising (are calculated using total organic carbon TOC
Current efficiency), electro-catalysis process is in Charge controlled stage (i.e. load transfer process is rate determining step), and current efficiency is protected at this time
Hold is 100%.When actual current density is in jlimWhen upper, the number of electrons for indicating that electro-catalysis system provides can have handled
Machine object molecule complete oxidation or mineralising, having the electronics having more at this time can use for side reactions such as analysis oxygen, electro-catalysis process
In mass transport limitation stage (i.e. mass transport process is rate determining step), current efficiency is lower than 100% at this time.
If using constant current mode (or pulse constant current mode, refer to current value do not change, only led in the set time or
Disconnected situation) it degrades, it is assumed that given current density value i0It is just the limit corresponding to the initial organic concentration of solution
Current density value jlim, then belonging to the stage of current efficiency very high (close to 100%) in the initial stage of reaction；Once reaction
A period of time is carried out, solution C OD/TOC value with reaction can reduce, it means that some time point upon start
On, limiting current density value j corresponding to solution C OD/TOC valuelim' it is less than i0Value, reaction will enter mass transport limitation rank
Section, current efficiency decline (are lower than 100%).For the angle of current efficiency, this be clearly it is unfavorable, will cause the volume of energy consumption
Outer consumption (analysis oxygen side reaction increases).
In fact, the size and electric current presentation mode of current density value all have very greatly the electrocatalytic oxidation process of organic matter
Influence.Reasonable combined running mode can effectively improve the efficiency of Electrocatalysis Degradation and reduce energy consumption.
Summary of the invention
The purpose of the present invention is to provide the dynamic currents in a kind of electrocatalytic oxidation to regulate and control method, passes through dynamic current tune
Integral pattern, to solve the problems, such as that current efficiency during organic matter electrocatalytic oxidation is low, power consumption values are high.
To achieve the above object, this discovery uses following technical scheme:
Dynamic current in electrocatalytic oxidation regulates and controls method, comprising the following steps:
1) according to the electro-catalysis system of actual motion calculate it corresponding to mass tranfer coefficient km；
2) during reacting progress, the actual value of the COD or TOC of solution are detected；
3) limiting current density value j corresponding to COD the or TOC value of etching solution at this time is calculatedlim；
4) gained limiting current density value j is calculated according to step 3)lim, come in conjunction with the annode area of electro-catalysis system used
Obtain corresponding current value, and this moment or the current value of subsequent time with this current value adjustment electro-catalysis system.
Further, limiting current density value j is calculated by formula (1) in step 3)lim:
jlim=4FkmCOD0 (1)
Wherein, jlimFor limiting current density value, unit Am–2；F is Faraday constant, value 96487Cmol–1；kmFor mass tranfer coefficient, unit ms–1；COD0For the initial COD value of solution, unit mgL-1。
Further, intermittent detection solution C OD or TOC value in step 2)；Step 3) is according to the intermittent detection of step 2)
COD the or TOC value of acquisition calculates corresponding limiting current density value jlim；Step 4) obtains limiting current density according to step 3)
Value jlimIntermittent adjustment subsequent time current value.
Further, continous way detects solution C OD or TOC value in step 2)；Step 3) is detected according to step 2)
COD or TOC value calculates corresponding limiting current density value j in real timelim；Step 4) obtains limiting current density value according to step 3)
jlimAdjustment current value in real time.
Further, electro-catalysis system uses constant pressure powering mode, constant current power mode or pulse power supply mode.
Further, mass tranfer coefficient kmIt needs to be tested according to the electro-catalysis system of actual motion, and is directed to COD value
It is worth mass tranfer coefficient to be distinguishing with TOC.
Further, detection solution C OD or TOC value is segmented into intermittent detection and continous way detection.
It further, can be using intermittent " detection-feedback-adjusting " when interval detects solution C OD/TOC value
Operational mode when starting degradation, obtains corresponding limiting current density value according to the initial COD/TOC value of solution, and with this value
Carry out Electrocatalysis Degradation；After running a period of time, solution C OD/TOC value is detected, obtains corresponding limiting current density value this moment,
It is adjusted, reruns lower a period of time；In cycles, until reaching processing target.Between two primary current adjustment movement
In time, current efficiency can be gradually reduced.
When further, using the operational mode of intermittent " detection-feedback-adjusting ", two primary current adjustment act it
Between time can optimize according to the actual situation.
It further, can be using continous way " detection-feedback-adjusting " when continuously detection solution C OD/TOC value
Operational mode is realized the real-time monitoring of solution C OD/TOC value, is passed through that is, under corresponding external hardware and software condition auxiliary
Corresponding system completes the calculating of corresponding carrying current value and completes the real-time monitoring to current value, so that current efficiency is stable always
Maintain 100% high level operation.
Further, intermittent or continous way operational mode no matter is used, power supply mode can choose constant pressure power supply mould
Formula, constant current power mode and pulse power supply mode.
Further, if selection constant pressure powering mode, used voltage swing can carry out according to the actual situation
Optimization.
Further, if selection constant current power mode, used current density size can be according to the actual situation
It optimizes.
Further, if strobe pulse powering mode, pulse frequency, duty ratio size, whether have negative pulse and its
The correlative factors such as size can optimize according to the actual situation.
Compared with the existing technology, the invention has the following advantages:
(1) core of dynamic current adjustment modes is so that the electrocatalytic oxidation process of organic matter is in practical electricity always
Current density is run in the state of being equal or slightly larger than limiting current density.It can effectively ensure that electro-catalysis system entire in this way
It is run in operational process with the current efficiency equal or close to 100%, great energy saving, while can guarantee the effect of processing
Fruit.
(2) when electric current provides, the electrochemical reaction at Cathode/Solution Interface is carried out；With the extension of time, electrode table
The diffusion layer in face initially forms and increases.The formation meeting of diffusion layer is so that the substance in solution bulk enters Cathode/Solution Interface
Layer encounters difficulties, and becomes rate determining step in some cases.If diffusion layer can be at any time under constant current (constant pressure) mode
Passage and constantly thicken, the influence of (or even fatal degree) to a certain degree is caused to reaction.In contrast to this, in pulse mode
Under formula, the offer time of electric current is very short (length of time artificially controls).Within the so short time, diffusion layer is difficult after being formed
Quickly thicken, then will due to electric current disconnection and disappear；Then, the various substances in solution bulk can smoothly enter into electricity
At pole/solution interface (organic pollutant entrance), the substance at Cathode/Solution Interface also can diffuse into solution bulk (reaction
The diffusion of intermediate product) so that material concentration is consistent with bulk solution.Then, electric current starts to provide again, and electrochemical reaction is opened again
Begin to carry out, so be recycled.It follows that pulse mode is for the diffusion problem during alleviation (or even solution) electro-catalysis
(i.e. mass transfer obstacle) has preferable help.Further, since pulse process is the state disconnected in electric current for some time, therefore
From the perspective of energy consumption, also there is certain advantage.
Specific embodiment
Embodiment 1: the intermittent electric current adjustment modes under constant current mode
The organic matter electrocatalytic oxidation system fixed for one, mass tranfer coefficient kmBe it is fixed, according to corresponding side
Foundation after method measures occurrence, as the calculating of subsequent limiting current density value.When starting degradation, the initial COD of test solution
Or TOC value, corresponding limiting current density value is obtained, and carry out electro-catalysis drop using this value as the current density value of constant current mode
Solution；After operation a period of time (such as 30min), solution C OD or TOC value is detected again, is obtained corresponding limiting current density value, is carried out
Adjustment runs the second segment time；Hereafter it is constantly adjusted in the same way, until the reaction is complete.Current value adjustment twice is dynamic
Time interval between work can optimize according to the actual situation.
Embodiment 2: the intermittent electric current adjustment modes under pulse mode
The mass tranfer coefficient k of degradation system is obtained by testm.When starting degradation, the initial COD or TOC value of test solution,
Corresponding limiting current density value is obtained, and carries out electro-catalysis drop using this value as the current density value of pulse mode direct impulse
Solution；After operation a period of time (such as 30min), solution C OD or TOC value is detected again, is obtained corresponding limiting current density value, is carried out
Adjustment runs the second segment time；Hereafter it is constantly adjusted in the same way, until the reaction is complete.Current value adjustment twice is dynamic
Time interval between work can optimize according to the actual situation.Pulse frequency, the duty ratio size, negative pulse of pulse mode
The correlative factors such as size can optimize according to the actual situation.
Embodiment 3: the continous way electric current adjustment modes under constant current mode
The mass tranfer coefficient k of degradation system is obtained by testm.Using the operation mould of continous way " detection-feedback-adjusting "
Formula is degraded with constant current mode that is, from starting degradation, by monitoring device real-time monitoring solution C OD or TOC value, passes through control
After system conversion processed, electric current adjustment instruction is issued to DC power supply, completes the real-time monitoring to current value, so that degradation process
Current efficiency is stably maintained at always 100% high level operation.
Embodiment 4: the continous way electric current adjustment modes under pulse mode
The mass tranfer coefficient k of degradation system is obtained by testm.Using the operation mould of continous way " detection-feedback-adjusting "
Formula degrades in a pulsed mode that is, from starting degradation, by monitoring device real-time monitoring solution C OD/TOC value, passes through control
After system conversion, electric current adjustment instruction is issued to the pulse power, completes the real-time monitoring to forward pulse current value, so that degradation
The current efficiency of process is stably maintained at always 100% high level operation.
Claims (3)
1. the dynamic current in electrocatalytic oxidation regulates and controls method, which comprises the following steps:
1) according to the electro-catalysis system of actual motion calculate it corresponding to mass tranfer coefficient km；
2) during reacting progress, the actual value of the COD or TOC of solution are detected；
3) limiting current density value j corresponding to COD the or TOC value of etching solution at this time is calculatedlim；
4) gained limiting current density value j is calculated according to step 3)lim, obtained in conjunction with the annode area of electro-catalysis system used
Corresponding current value, and this moment or the current value of subsequent time with this current value adjustment electro-catalysis system；
Limiting current density value j is calculated by formula (1) in step 3)lim:
jlim=4FkmCOD0 (1)
Wherein, jlimFor limiting current density value, unit Am–2；F is Faraday constant, value 96487Cmol–1；km
For mass tranfer coefficient, unit ms–1；COD0For the initial COD value of solution, unit mgL-1；
Electro-catalysis system uses constant pressure powering mode, constant current power mode or pulse power supply mode.
2. the dynamic current in electrocatalytic oxidation according to claim 1 regulates and controls method, which is characterized in that step 2) is intermediate
Formula of having a rest detects solution C OD or TOC value；Step 3) calculates corresponding pole according to the intermittent detected COD or TOC value of step 2)
Threshold currents density value jlim；Step 4) obtains limiting current density value j according to step 3)limIntermittent adjustment subsequent time electric current
Value.
3. the dynamic current in electrocatalytic oxidation according to claim 1 regulates and controls method, which is characterized in that connect in step 2)
Continuous formula detects solution C OD or TOC value；Step 3) calculates the corresponding limit according to the detected COD or TOC value of step 2) in real time
Current density value jlim；Step 4) obtains limiting current density value j according to step 3)limAdjustment current value in real time.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102323999A (en) * | 2011-10-12 | 2012-01-18 | 中国石油化工股份有限公司 | Rod-pumped well energy-saving potential measuring method |
| CN103970986A (en) * | 2014-04-09 | 2014-08-06 | 上海申瑞继保电气有限公司 | Calculating method of energy utilization efficiency of cogeneration cooling heating and power equipment |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102323999A (en) * | 2011-10-12 | 2012-01-18 | 中国石油化工股份有限公司 | Rod-pumped well energy-saving potential measuring method |
| CN103970986A (en) * | 2014-04-09 | 2014-08-06 | 上海申瑞继保电气有限公司 | Calculating method of energy utilization efficiency of cogeneration cooling heating and power equipment |
Non-Patent Citations (3)
| Title |
|---|
| Anodic oxidation of 2-naphthol at boron-doped diamond electrodes;Panizza M等;《 Journal of Electroanalytical Chemistry》;20011231;第507卷(第12期);第206-214页 |
| Oxidation tion of 4-chlorophenol at boron-doped diamond electrodes for wastewater treatment;Ｒodrigo M．A等;《 Journal of the ElectrochemicalSociety》;20011231;第148卷(第5期);第60-64页 |
| TiO2-AC电催化氧化含酚废水;李鹏等;《环境工程学报》;20141105;第8卷(第11期);第1.3、2.3、2.4节 |
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