CN104532259B - The composite electrochemical device protected for condenser pipe series cathode - Google Patents
The composite electrochemical device protected for condenser pipe series cathode Download PDFInfo
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- CN104532259B CN104532259B CN201410824028.7A CN201410824028A CN104532259B CN 104532259 B CN104532259 B CN 104532259B CN 201410824028 A CN201410824028 A CN 201410824028A CN 104532259 B CN104532259 B CN 104532259B
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Abstract
A kind of composite electrochemical device protected for condenser pipe series cathode; combined type iron anode is provided with the blind end of the shell of condenser; insulation board is provided with the relative both sides of combined type iron anode; the insulation board of side is arranged on the inside of the blind end of shell, and auxiliary cathode is housed outside the insulation board of opposite side；Equipped with a reference electrode for being used to detect constant potential value near tube sheet in hydroecium；Described shell, combined type iron anode, reference electrode and auxiliary cathode is connected with the corresponding output end of control device respectively.It is an advantage of the invention that：Using ferroalloy anode impressed current cathodic protection method and electrolysis iron anode film forming Combined Protection, each separately protected existing all problems can be fully solved.There is wide popularizing application prospect in terms of the etching problem of power plant and ship condenser copper alloy pipeline is solved, while the cost of raw material can be saved greatly.
Description
Technical field
It is that one kind can implement additional the present invention relates to a kind of composite electrochemical device protected for condenser pipe series cathode
Current cathodic protection is electrolysed the composite electrochemical device for producing iron ion simultaneously.It is mainly used in the corrosion of power plant or ship condenser
Protection.
Background technology
Condenser is one of important component of power plants generating electricity unit, once broken down because of corrosion failure, will
Whole compressor emergency shutdown is caused to stop production.The condenser pipe of condenser is generally made of copper alloy.Hydroecium wall is generally manufactured using titanium steel, pipe
Plate material is generally manufactured with carbon steel, and tube sheet material is generally manufactured with carbon steel or one-ton brass.Due to xenogenesis such as tube bank, tube sheet and hydroeciums
The galvanic corrosion of metal is acted on, the influence of the factor such as impingment corrosion effect of turbulent cooling water, causes condenser to turn into power plant rotten
One of breakage event occurrence frequency highest device is lost, therefore the etching problem of condenser receives great attention.Using the moon
Pole protection can significantly control steel hydroecium, tube sheet and the corrosion for condensing pipe end.Ferrous sulfate uses condenser extensively into film process
The corrosion protection of copper alloy cooling tube.Found that iron ion has protective effect to copper pipe in water early in 1940.Nineteen fifty-five the U.S. first
Ferrous sulfate processing is implemented to power plant condenser pipe.Many countries, which have all carried out ferrous sulfate, afterwards prevents grinding for Copper Tube Corrosion
Study carefully, the corrosion protection until being still used for power plant's gas trap and ship condenser tube at present.
Ferroelectricity solution film forming with Faradaic current control, anode consumption with ferrous ion concentration due to that can use accumulation electricity
Prediction, fouling can be eliminated by dipole inversion, the advantages of operation is simple, ferrous sulfate method is replaced with it with very wide
Wealthy prospect.Although electrolysis iron ion film forming has many advantages than ferrous sulfate film forming, simple electrolysis iron ion film forming,
In turbulent serious place, sulphide staining seawater, in the case that pipeline may have the deposits such as mud, iron ion quality of forming film may
It cannot be guaranteed.The place of desirable is not reached in quality of forming film, it is possible to create etching problem.
Typically in power plant or ship condenser, in order to the iron water chamber head in the structure, copper alloy tubulation road with
And tube sheet is protected, the electrochemical cathodic protection method such as impressed current method or sacrificial anode protection is employed.But only with list
Pure cathode protecting process, the shielding action due to copper alloy tube tube wall to electric current, protective current is difficult to go deep into the middle part of copper pipe, arriving
Up to being limited in scope, it is difficult for making to be obtained protecting effect completely by protective.Existing impressed current cathodic protection system can not
The rich iron film that the effect of being effectively protected is played to copper alloy condenser pipe road is formed on copper alloy pipeline inner wall.Must individually it use
The iron ion supply method of the iron ion generating means of input ferrous sulfate or installation iron anode forms rich iron in copper alloy tube wall
Film.The implementation that ferrous sulfate is put into Practical Project is difficult, and is likely to cause pollution.Using install electrolytic iron from
Sub- generating means, circuit control system sets the circuit for applying the optimal current potential of electrochemical cathodic protection and sets electrolytic iron respectively
The circuit that ion occurs, each circuit is individually controlled, to reach optimum condition.But because electrochemical cathodic protection circuit and iron from
It is separated that circuit, which occurs, for son, therefore the device has the problem of control is numerous and diverse, time-consuming.
The content of the invention
It is an object of the present invention to provide a kind of composite electrochemical device protected for condenser pipe series cathode, to solve existing skill
The above-mentioned various problems that art is present.
The technical scheme is that：A kind of composite electrochemical device protected for condenser pipe series cathode, including condensation
Device, the condenser includes shell, tube sheet and cooling tube, and the tube sheet of Copper alloy material is arranged in the shell of mild steel material, in pipe
The cooling tube of Copper alloy material is housed in each hole of plate, hydroecium is constituted between tube sheet and the blind end of shell, in hydroecium
Side is provided with rubber lining, it is characterised in that combined type iron anode is provided with the blind end of described shell, in combined type iron anode
Relative both sides be provided with insulation board, the insulation board of side is arranged on the inside of the blind end of shell, the insulation board exterior of opposite side
There is auxiliary cathode；Equipped with a reference electrode for being used to detect constant potential value near tube sheet in hydroecium；Described shell,
Combined type iron anode, reference electrode and auxiliary cathode are connected with the corresponding output end of control device respectively.
Described combined type iron anode is formed by insoluble Magnetic Iron Oxide Anode and mild steel anode combination, mild steel annulus sun
Pole is enclosed on the outer peripheral face of insoluble Magnetic Iron Oxide Anode.
Described combined type iron anode is cylinder, and its two ends is provided with described insulation board；In the insoluble magnetic of cylinder
Property oxidation iron anode the described mild steel annulus anode of outer peripheral face suit.
Described mild steel annulus anode is enclosed on magnetic iron oxide rod anode by the superposition of multiple mild steel annulus, blending bolt
Interfixed with nut.
Described control device is made up of constant potential impressed current cathodic protection loop and constant-current electrolysis loop, constant potential
Impressed current cathodic protection loop is mainly used to make all components of Water in Condenser chamber interior obtain cathodic protection, and constant-current electrolysis is returned
Road makes copper alloy surface form rich iron diaphragm for producing enough iron ions.
Described constant-current electrolysis loop include constant current circuit transformer, current control loop, constant current controlling circuit,
Constant current circuit rectifier, auxiliary cathode current detector and total current detector, secondary one of constant current circuit transformer
End is connected after passing through current control loop with an input of constant current circuit rectifier, the secondary of constant current circuit transformer
The other end be connected with another input of constant current circuit rectifier, the cathode output end of constant current circuit rectifier is successively
It is connected after series connection auxiliary cathode current detector and total current detector with described combined type iron anode pole, constant current circuit is whole
The cathode output end of stream device is connected with described auxiliary cathode；The current output terminal of current control loop and constant current controlling circuit
Input connection, the two ends of two output ends of constant current controlling circuit respectively with total current detector are connected；
Described constant potential impressed current cathodic protection loop includes potentiostatic circuit transformer, potentiostatic circuit rectification
Device, potentiostatic deposition current detector and constant potential control circuit, potentiostatic circuit transformer secondary output two ends respectively with constant potential
Two inputs connection of rectifier, cathode output end and the potentiostatic deposition current detector of potentiostatic circuit rectifier
The input connection of circuit, the output end of potentiostatic deposition current detector and described total current detector are controlled with constant potential
Input connection, constant potential control circuit two output ends be connected respectively with described shell and reference electrode；Constant potential
The cathode output end and cage connection of rectifier.
Described control device uses multichannel potentiostat.
It is an advantage of the invention that：Using combined type anode impressed current cathodic protection method and electrolysis iron anode film forming joint
Protection, can be fully solved each separately protected existing all problems, not only give full play to respective advantage, and both
Have the advantages that to be consistent and coordinate.Electrolysis iron ion film forming protection can not only protect cathode protecting process protection less than pipeline section and
Steel, and due to the formation of rich iron film, the resistance of copper alloy surface is added, so as to reduce condenser cathodic protection institute
Current density is needed, the pipe protection distance of impressed current cathodic protection can also be extended.Cathodic protection can not only be protected
Iron ion quality of forming film is bad and lacks the place of protection, and result of study shows, 0.1mA/m2Tiny cathodes protection electricity
Stream can just promote the formation of rich iron film, improve the quality of forming film of iron ion.Therefore, the invention is solving power plant and ship condensation
There is wide popularizing application prospect in terms of the etching problem of device copper alloy pipeline, at the same can greatly save raw material into
This, without replacing copper alloy condenser pipe material from expensive precious metal material.
Brief description of the drawings
Fig. 1 is the structural representation of present invention installation within the condenser；
Fig. 2 is the theory diagram of automatic control type protection device.
Description of reference numerals：A-condenser, 1-（Condenser）Shell, 2-tube sheet, 3-cooling tube, 4-auxiliary cathode,
5-combined type iron anode, 6-insulation board, 7-control device, 8-reference electrode, 9-AC power（Input）, 10-permanent
Current circuit transformer, 11-current control loop, 12-constant current controlling circuit, 13-constant current circuit rectifier, 14-
Auxiliary cathode current detector, 15-total current detector, 16-potentiostatic circuit rectifier, the inspection of 17-potentiostatic deposition electric current
Survey device, 18-constant potential control circuit, 19-potentiostatic circuit transformer.
Embodiment
Referring to Fig. 1 and Fig. 2, a kind of composite electrochemical device protected for condenser pipe series cathode, including condenser A should
Condenser A includes shell 1, tube sheet 2 and cooling tube 3, and the tube sheet 2 of Copper alloy material is arranged in the shell 1 of mild steel material, in pipe
The cooling tube 3 of Copper alloy material is housed in each hole of plate 2, hydroecium 20 is constituted between tube sheet 2 and the blind end of shell 1, in water
The inner side of room 20 is provided with rubber lining 21.Combined type iron anode 5 is provided with the blind end of described shell 1, in combined type iron sun
The relative both sides of pole 5 are provided with insulation board 6, and the insulation board 6 of side is arranged on the inside of the blind end of shell 1, the insulation of opposite side
Plate 6 is outer to be equipped with auxiliary cathode 4（In the through hole for being supported on the center of combined type iron anode 5）.It is equipped near tube sheet 2 in hydroecium 20
One reference electrode 8 for detecting constant potential value；Described shell 1, combined type iron anode 5, reference electrode 8 and auxiliary the moon
Pole 4 is connected with the corresponding output end of a control device 7 respectively.
Described combined type iron anode 5 by（It is insoluble）Magnetic Iron Oxide Anode 51 and mild steel anode 52 are combined, and two
Partial material is current material.Combined type iron anode 5 is cylinder, and combination is by the less mild steel circle of multiple quality
Ring superposition is enclosed on the outer peripheral face of the Magnetic Iron Oxide Anode 51 of cylinder, and is fixedly secured with customization bolt and nut, and makes magnetic
Property the exposure of oxidation iron anode 51 end active surface meet the need of condenser hydroecium and tube sheet impressed current cathodic protection design
Will.Combined type iron anode 5 is arranged in water chamber head and insulated with hydroecium wall.The structure of combined type iron anode 5 can be greatly improved
Service life.
Described control device 7 is made up of constant-current electrolysis loop 71 and constant potential impressed current cathodic protection loop 72
（Secondary Fig. 2）.
The constant-current electrolysis loop 71 includes constant current circuit transformer 10, current control loop 11, constant current controlling electricity
Road 12, constant current circuit rectifier 13, auxiliary cathode current detector 14 and total current detector 15, constant current circuit transformer
10 secondary one end is connected by an input after current control loop 11 with constant current circuit rectifier 13, constant current
The secondary other end of circuit transformer 10 is connected with another input of constant current circuit rectifier 13, and constant current circuit is whole
The cathode output end of stream device 13 is sequentially connected in series after auxiliary cathode current detector 14 and total current detector 15（E ends）With it is described
Combined type iron anode 5 is connected, the cathode output end of constant current circuit rectifier 13（D ends）It is connected with described auxiliary cathode 4；Electricity
The current output terminal in flow control loop 11 is connected with the input of constant current controlling circuit 12, two of constant current controlling circuit 12
Two ends of the output end respectively with total current detector 15 are connected.
The constant potential impressed current cathodic protection loop 72 includes potentiostatic circuit transformer 19, potentiostatic circuit rectifier
16th, potentiostatic deposition current detector 17 and constant potential control circuit 18,19 level two ends of potentiostatic circuit transformer respectively with
Two inputs connection of potentiostatic circuit rectifier 16, the cathode output end and potentiostatic deposition of potentiostatic circuit rectifier 16
The input connection of current detector 17 and constant potential control circuit 18, the output end of potentiostatic deposition current detector 17 and institute
The input connection for the total current detector 15 stated, constant potential controls two output ends of circuit 18（B ends and c ends）Respectively with institute
The shell 1 and reference electrode 8 stated are connected；The cathode output end of potentiostatic circuit rectifier 16（A ends）With condenser hydroecium or pipe
Plate is connected.
Constant-current electrolysis loop 71 provides electric current needed for electrolysis iron ion film forming, and constant potential loop maintains suitably protecting current potential
Required electric current.The positive pole e in constant-current electrolysis loop 71 is connected with combined type iron anode 5, and negative pole d is connected with auxiliary cathode 4, specially
For being electrolysed combined type iron anode 5（The mild steel anode 52 of outer peripheral face）It is set to produce iron ion.Constant potential impressed current negative electrode is protected
Protect the positive pole in loop 72 and the positive pole of the output end of constant-current electrolysis loop 71（Auxiliary cathode current detector 14 is detected with total current
Contact between device 15）It is connected, by being connected again with combined type iron anode 5 after total current detector 15, negative pole a and hydroecium wall
（Shell 1）It is connected, for making hydroecium inwall cathodic polarization protection potential value needed for.I.e. by combined type iron anode 5 flow out it is total
Electric current i3The overwhelming majority（i1）Auxiliary cathode 4 is flowed to, electrolysis combined type iron anode 5 is specifically used to（Mild steel anode 52）Produce it
Iron ion, portion of electrical current（i2）Hydroecium and pipe are flowed to by the insoluble Magnetic Iron Oxide Anode 51 inside combined type iron anode 5
There is provided cathodic protection effect for plate 2.
The present invention operation principle be：
Reference electrode 8 is fixed on tube sheet surface or hydroecium wall near it, for detecting and controlling the protection electricity of hydroecium
Position.
Detected with reference electrode 8 by protective（Condenser）Current potential, control output current with control device 7.At this
In device, the protection potential that will be detected with reference electrode 8, automatically control is maintained at predetermined current potential, reaches optimal
Electro-chemical protection.Meanwhile, the protection potential that will be detected with reference electrode 8, automatically control electric current holding is predetermined
Value, the iron concentration for producing dissolving keeps constant, so operation that need not be complicated, can significantly extend condenser tube
The life-span on road.As previously discussed, using the present invention can obtain it is simple in construction, operation easily, protecting effect it is extraordinary additional
Current protective device, and reach the protecting effect for being industrially conducive to wide popularization and application.
The present invention invents the corrosion protection for power plant or ship condenser.By external current protection device, electrolytic iron sun
Pole, by protective negative electrode, separately set auxiliary cathode, detect by the reference electrode of protection bulk potential, connect these electrodes and protected
Body also serves as power supply and made constant and protective current and auxiliary cathode electric current sum are controlled in steady state value by the current potential of protective
Constant potential constant current device constituted, it is simple to operate, can obtain simultaneously electrochemical protection effect and electrolysis iron ion protect
The effect of shield.Using ferroalloy anode impressed current cathodic protection method in the present invention and electrolysis iron anode film forming Combined Protection,
Each separately protected existing all problems can be then fully solved, respective advantage, and both tools are not only given full play to
Have the advantages that to be consistent and coordinate.
The present invention be based on above-mentioned viewpoint, research and develop for condenser to impressed current electrochemical protect and using iron from
The protection of son and, overall structure is simple, operation easily, and the good composite electrochemical protection device of real work effect.
Obtain following result：
（1）In order to reach best protection effect, use can automatically control the protective current to protective and will be protected
The current potential of body is maintained at the constant current constant potential automatic control type protection device of predetermined potential.
（2）The automatic control type protection device except by protective as negative electrode in addition to it is another negative electrode is set, will be by protective current
Keep constant with flowing into the electric current sum of auxiliary cathode, then can ensure that the iron ion of constant basis, and adjust as needed, to iron
Ionic weight can be controlled simply.
（3）Only using the electric current of general impressed current cathodic protection（10-15A）, it is impossible to obtain the iron of full concentration from
Son.
（4）The present invention is made based on above-mentioned conclusion, it is characterized in that：Closed by impressed current catholic protection device, iron
Gold electrode, by protective negative electrode, separately set auxiliary cathode, detect by the reference electrode of protection bulk potential, connect these electrodes and by
Protective also serves as power supply and made constant and protective current and auxiliary cathode electric current sum are controlled in perseverance by the current potential of protective
The constant potential constant current device of definite value is constituted, operate it is very simple, can obtain simultaneously impressed current cathodic protection effect with
And the effect of electrolysis iron ion film forming protection.
Described control device 7 uses existing multichannel potentiostat（For example：Biologic VWP3）, can be simultaneously
Realize that constant potential constant current circuit is automatically controlled.
Claims (4)
1. a kind of composite electrochemical device protected for condenser pipe series cathode, including condenser, the condenser include shell, pipe
Plate and cooling tube, the tube sheet of Copper alloy material are arranged in the shell of mild steel material, and copper alloy is housed in each hole of tube sheet
Hydroecium is constituted between the blind end of the cooling tube of material, tube sheet and shell, rubber lining is provided with the inner side of hydroecium, its feature exists
In, combined type iron anode is provided with the blind end of described shell, insulation board is provided with the relative both sides of combined type iron anode,
The insulation board of side is arranged on the inside of the blind end of shell, and auxiliary cathode is housed outside the insulation board of opposite side；Pipe in hydroecium
Equipped with a reference electrode for being used to detect constant potential value near plate；Described shell, combined type iron anode, reference electrode and
Auxiliary cathode is connected with the corresponding output end of control device respectively；Described combined type iron anode is by insoluble magnetic iron oxide sun
Pole and mild steel anode combination are formed, outer peripheral face of the mild steel annulus anode jacket in insoluble Magnetic Iron Oxide Anode；Described is compound
Formula iron anode is cylinder, and its two ends is provided with described insulation board；In the periphery of the insoluble Magnetic Iron Oxide Anode of cylinder
The described mild steel annulus anode of surface cover dress；Described mild steel annulus anode is enclosed on magnetic oxygenated iron staff by the superposition of multiple mild steel annulus
On shape anode, blending bolt and nut interfix.
2. the composite electrochemical device according to claim 1 protected for condenser pipe series cathode, it is characterised in that described
Control device be made up of constant potential impressed current cathodic protection loop and constant-current electrolysis loop, constant potential impressed current negative electrode
Protective loop is mainly used to make all components of Water in Condenser chamber interior obtain cathodic protection, and constant-current electrolysis loop is used for producing foot
Enough iron ions make copper alloy surface form rich iron diaphragm.
3. the composite electrochemical device according to claim 2 protected for condenser pipe series cathode, it is characterised in that described
To include constant current circuit transformer, current control loop, constant current controlling circuit, constant current circuit whole in constant-current electrolysis loop
Device, auxiliary cathode current detector and total current detector are flowed, secondary one end of constant current circuit transformer passes through electric current control
It is connected behind loop processed with an input of constant current circuit rectifier, the secondary other end and the perseverance of constant current circuit transformer
Another input connection of current circuit rectifier, the cathode output end of constant current circuit rectifier is sequentially connected in series auxiliary cathode
It is connected after current detector and total current detector with described combined type iron anode pole, the negative pole of constant current circuit rectifier is defeated
Go out end to be connected with described auxiliary cathode；The current output terminal of current control loop connects with the input of constant current controlling circuit
Connect, the two ends of two output ends of constant current controlling circuit respectively with total current detector are connected；Powered up outside described constant potential
Flowing cathodic protection loop includes potentiostatic circuit transformer, potentiostatic circuit rectifier, potentiostatic deposition current detector and perseverance
Potential control circuit, potentiostatic circuit transformer secondary output two ends are connected with two inputs of potentiostatic circuit rectifier respectively,
The input of the cathode output end of potentiostatic circuit rectifier and potentiostatic deposition current detector and constant potential control circuit connects
Connect, the output end of potentiostatic deposition current detector is connected with the input of described total current detector, constant potential control electricity
Two output ends on road are connected with described shell and reference electrode respectively；The cathode output end of potentiostatic circuit rectifier with it is outer
Shell is connected.
4. the composite electrochemical device according to claim 1 protected for condenser pipe series cathode, it is characterised in that described
Control device use multichannel potentiostat.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410824028.7A CN104532259B (en) | 2014-12-26 | 2014-12-26 | The composite electrochemical device protected for condenser pipe series cathode |
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|---|---|---|---|
| CN201410824028.7A CN104532259B (en) | 2014-12-26 | 2014-12-26 | The composite electrochemical device protected for condenser pipe series cathode |
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| CN104532259B true CN104532259B (en) | 2017-10-20 |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106990742B (en) * | 2017-06-02 | 2023-07-21 | 天津隆顺技术服务有限公司 | Anti-corrosion protection linkage control device and system by reverse potential method |
| CN109706457B (en) * | 2017-10-26 | 2023-10-20 | 江苏启能新能源材料有限公司 | Electronic anode protection anti-corrosion device and method for phase change heat storage equipment |
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| CN1376213A (en) * | 1998-10-29 | 2002-10-23 | 福斯洛克国际有限公司 | Connector for use in cathodic protection and method of use |
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| CN201154989Y (en) * | 2008-01-16 | 2008-11-26 | 青岛双瑞防腐防污工程有限公司 | Platinum-niobium composite silk-shaped auxiliary anode |
| CN201158711Y (en) * | 2008-01-16 | 2008-12-03 | 青岛双瑞防腐防污工程有限公司 | Platinum-tantalum netted auxiliary anode for harbor work |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55122882A (en) * | 1979-03-13 | 1980-09-20 | Nippon Boshoku Kogyo Kk | Outside power source type corrosion-preventive apparatus |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1201080A (en) * | 1997-06-03 | 1998-12-09 | 福建炼油化工有限公司 | Method for preventing carbon-steel cooling apparatus from corrosion by sea water and apparatus thereof |
| CN1376213A (en) * | 1998-10-29 | 2002-10-23 | 福斯洛克国际有限公司 | Connector for use in cathodic protection and method of use |
| CN101100751A (en) * | 2007-07-18 | 2008-01-09 | 中国船舶重工集团公司第七二五研究所 | Long life ferroalloy sacrificial anode |
| CN201154989Y (en) * | 2008-01-16 | 2008-11-26 | 青岛双瑞防腐防污工程有限公司 | Platinum-niobium composite silk-shaped auxiliary anode |
| CN201158711Y (en) * | 2008-01-16 | 2008-12-03 | 青岛双瑞防腐防污工程有限公司 | Platinum-tantalum netted auxiliary anode for harbor work |
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