CN104532259A - Compound electrochemical device for condenser cathode protection - Google Patents
Compound electrochemical device for condenser cathode protection Download PDFInfo
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- CN104532259A CN104532259A CN201410824028.7A CN201410824028A CN104532259A CN 104532259 A CN104532259 A CN 104532259A CN 201410824028 A CN201410824028 A CN 201410824028A CN 104532259 A CN104532259 A CN 104532259A
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Abstract
The invention relates to a compound electrochemical method for condenser cathode protection. A compound iron anode is arranged at the closed end of the housing of a condenser, an insulation board is arranged on each of two opposite sides of the compound iron anode, the insulation board on one side is mounted on the inner side of the closed end of the housing, and an auxiliary cathode is mounted outside the insulation board on the other side; a reference electrode used for detecting the constant potential value is mounted near a tube plate in a water chamber; the housing, the compound iron anode, the reference electrode and the auxiliary cathode are respectively connected with corresponding output terminals of a control device. The compound electrochemical method has the advantages that the ferroalloy anode impressed current cathode protection method and electrolytic iron anode film are adopted for combined protection, so that all problems caused by respectively independent protection are completely solved; and in the aspect of solving the corrosion problem of condenser copper alloy pipelines of both power plants and ships, a wide popularization and application prospect is achieved, and the raw material cost is greatly lowered.
Description
Technical field
The present invention relates to a kind of composite electrochemical device for the protection of prolong series cathode, is a kind of composite electrochemical device that can produce iron ion in execution impressed current cathodic protection electrolysis simultaneously.Be mainly used in the corrosion prevention of power plant or boats and ships condenser.
Background technology
Condenser is one of important component part of power plants generating electricity unit, once break down because of corrosion failure, whole compressor emergency shutdown will be caused to stop production.The prolong of condenser is made with copper alloy usually.Hydroecium wall adopts titanium steel manufacture usually, and tube sheet material uses carbon steel manufacture usually, and tube sheet material is usually with carbon steel or one-ton brass manufacture.Due to the galvanic corrosion effect of the dissimilar metals such as tube bank, tube sheet and hydroecium, the impact of the factors such as the impingement corrosion effect of turbulent flow water coolant, cause condenser to become one of the highest device of power plant's corrosion failure accident occurrence frequency, therefore the etching problem of condenser receives great attention.Adopt galvanic protection can control the corrosion of steel hydroecium, tube sheet and condensation pipe end significantly.The corrosion protection of condenser copper alloy cooling tube is extensively used in the process of ferrous sulfate film forming.Just find that as far back as 1940 in water, iron ion has provide protection to copper pipe.Nineteen fifty-five, the U.S. implemented ferrous sulfate process to power plant condenser pipe first.Many countries have all carried out the research that ferrous sulfate prevents Copper Tube Corrosion afterwards, until be still used to the corrosion prevention of power plant's steam trap and boats and ships condenser tube at present.
Owing to having, ferrous ion concentration can control with Faradaic current ferroelectric solution film forming, anode consumption can with accumulation power quantity predicting, can eliminate the advantages such as fouling, operation is simple by dipole inversion, replace ferrous sulfate method to have very wide prospect with it.Although electrolytic iron ion film forming has many advantages than ferrous sulfate film forming, simple electrolytic iron ion film forming, seriously locate at turbulent flow, in sulphide staining seawater, under pipeline may have the sedimental situations such as mud, iron ion quality of forming film may can not be guaranteed.Do not reach the place of desirable at quality of forming film, may etching problem be produced.
General in power plant or boats and ships condenser, in order to protect the iron water chamber head in this structure, copper alloy tubulation road and tube sheet, have employed the electrochemical cathodic protection such as impressed current method or sacrificial anode protection method.But only adopt simple cathode protecting process, because copper alloy tube tube wall is to the shielding effect of electric current, protective current not easily gos deep into the middle part of copper pipe, and coverage area is limited, it is difficult that protected body be made to obtain protected effect completely.Existing impressed current cathodic protection system can not form rich iron film copper alloy condenser pipe road being played to effective provide protection on copper alloy pipeline inner wall.The iron ion supply method of the iron ion generating unit dropping into ferrous sulfate or install iron anode must be adopted separately to form rich iron film at copper alloy tube wall.The enforcement dropping into ferrous sulfate in Practical Project is difficult, and likely pollutes.Adopt and install electrolytic iron ion generating device, circuit control system arranges the circuit applying the best current potential of electrochemical cathodic protection and the circuit arranging the generation of electrolytic iron ion respectively, and each circuit controls separately, to reach top condition.But because electrochemical cathodic protection circuit is what to separate with iron ion circuit for generating, therefore this device also exists numerous and diverse, the time-consuming problem of control.
Summary of the invention
The object of the invention is to provide a kind of composite electrochemical device for the protection of prolong series cathode, to solve the above-mentioned various problem that prior art exists.
Technical scheme of the present invention is: a kind of composite electrochemical device for the protection of prolong series cathode, comprise condenser, this condenser comprises shell, tube sheet and cooling tube, the tube sheet of copper alloy material is arranged in the shell of mild steel material, the cooling tube of copper alloy material is housed in each hole of tube sheet, hydroecium is formed between tube sheet and the blind end of shell, rubber lining is provided with in the inner side of hydroecium, it is characterized in that, combined type iron anode is provided with at the blind end of described shell, insulcrete is provided with in the relative both sides of combined type iron anode, the insulcrete of side is arranged on inside the blind end of shell, outside the insulcrete of opposite side, auxiliary cathode is housed, one is equipped with for detecting the reference electrode of 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 terminal of control device respectively.
Described combined type iron anode is formed by insoluble Magnetic Iron Oxide Anode and mild steel anode combination, and mild steel annulus anode jacket is at the periphery of insoluble Magnetic Iron Oxide Anode.
Described combined type iron anode is cylindrical, and its two ends are provided with described insulcrete; At the mild steel annulus anode described in the periphery suit of columniform insoluble Magnetic Iron Oxide Anode.
Described mild steel annulus anode is superposed by multiple mild steel annulus and is enclosed within martial ethiops rod anode, and interfixes with bolt and 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 galvanic protection, and constant-current electrolysis loop is used for producing enough iron ions makes copper alloy surface form rich iron protective membrane.
Described constant-current electrolysis loop comprises constant current circuit transformer, current control loop, constant current controlling circuit, constant current circuit rectifier, auxiliary cathode amperometric and total current detector, secondary one end of constant current circuit transformer is connected with an input terminus of constant current circuit rectifier by after current control loop, the secondary the other end of constant current circuit transformer is connected with another input terminus of constant current circuit rectifier, the cathode output end of constant current circuit rectifier auxiliary cathode amperometric of connecting successively is connected with described combined type iron anode pole with after total current detector, the cathode output end of constant current circuit rectifier is connected with described auxiliary cathode, the current output terminal of current control loop is connected with the input terminus of constant current controlling circuit, and two output terminals of constant current controlling circuit are connected with the two ends of total current detector respectively,
Described constant potential impressed current cathodic protection loop comprises potentiostatic circuit transformer, potentiostatic circuit rectifier, potentiostatic deposition amperometric and constant potential pilot circuit, potentiostatic circuit transformer secondary output two ends are connected with two input terminuss of potentiostatic circuit rectifier respectively, the cathode output end of potentiostatic circuit rectifier is connected with the input terminus of potentiostatic deposition amperometric and constant potential pilot circuit, the output terminal of potentiostatic deposition amperometric is connected with the input terminus of described total current detector, two output terminals of constant potential pilot circuit are connected with described shell and reference electrode respectively, the cathode output end of potentiostatic circuit rectifier is connected with shell.
Described control device adopts hyperchannel potentiostat.
Advantage of the present invention is: adopt combined type anode impressed current cathodic protection method and electrolytic iron anode film forming Combined Protection; respective separately protected existing all problems can be solved completely; not only give full play to respective advantage, and both has the advantage conforming to and coordinate.Electrolytic iron ion film forming protection not only can protect cathode protecting process protect less than pipeline section and steel; and due to the formation of rich iron film; add the resistance of copper alloy surface; thus reducing the required current density of condenser cathodic protection, the pipe protection distance of impressed current cathodic protection also can be extended.Galvanic protection not only can protect the place that shortage is protected iron ion quality of forming film is bad, and result of study shows, 0.1mA/m
2tiny cathodes protective current just can promote the formation of rich iron film, improve the quality of forming film of iron ion.Therefore, this invention has wide popularizing application prospect in the etching problem solving power plant and boats and ships condenser copper alloy pipeline, greatly can save material cost simultaneously, and expensive precious metal material need not be selected to replace copper alloy condenser pipe material.
Accompanying drawing explanation
Fig. 1 is the structural representation that the present invention installs within the condenser;
Fig. 2 is the functional block diagram of automatic control type protector.
Description of reference numerals: A-condenser, 1-(condenser) shell, 2-tube sheet, 3-cooling tube, 4-auxiliary cathode, 5-combined type iron anode, 6-insulcrete, 7-control device, 8-reference electrode, 9-AC power (input terminus), 10-constant current circuit transformer, 11-current control loop, 12-constant current controlling circuit, 13-constant current circuit rectifier, 14-auxiliary cathode amperometric, 15-total current detector, 16-potentiostatic circuit rectifier, 17-potentiostatic deposition amperometric, 18-constant potential pilot circuit, 19-potentiostatic circuit transformer.
Embodiment
See Fig. 1 and Fig. 2; a kind of composite electrochemical device for the protection of prolong series cathode; comprise condenser A; this condenser A comprises shell 1, tube sheet 2 and cooling tube 3; the tube sheet 2 of copper alloy material is arranged in the shell 1 of mild steel material; the cooling tube 3 of copper alloy material is housed in each hole of tube sheet 2, between the blind end of tube sheet 2 and shell 1, forms hydroecium 20, be provided with rubber lining 21 in the inner side of hydroecium 20.Combined type iron anode 5 is provided with at the blind end of described shell 1, insulcrete 6 is provided with in the relative both sides of combined type iron anode 5, the insulcrete 6 of side is arranged on inside the blind end of shell 1, auxiliary cathode 4(is housed outside the insulcrete 6 of opposite side and is supported in the through hole at combined type iron anode 5 center).One is equipped with for detecting the reference electrode 8 of constant potential value near tube sheet 2 in hydroecium 20; Described shell 1, combined type iron anode 5, reference electrode 8 and auxiliary cathode 4 are connected with the corresponding output terminal of a control device 7 respectively.
Described combined type iron anode 5 is combined by (insoluble) Magnetic Iron Oxide Anode 51 and mild steel anode 52, and two-part material is current material.Combined type iron anode 5 is cylindrical; array mode superposes by the mild steel annulus that multiple quality is less the periphery being enclosed within columniform Magnetic Iron Oxide Anode 51; and fixedly secure with customization bolt and nut, and the effective surface that Magnetic Iron Oxide Anode 51 end is exposed meets the needs of condenser hydroecium and tube sheet impressed current cathodic protection design.Combined type iron anode 5 to be arranged in water chamber head and to insulate with hydroecium wall.The structure of combined type iron anode 5 can improve work-ing life greatly.
Described control device 7 is made up of (secondary Fig. 2) constant-current electrolysis loop 71 and constant potential impressed current cathodic protection loop 72.
This constant-current electrolysis loop 71 comprises constant current circuit transformer 10, current control loop 11, constant current controlling circuit 12, constant current circuit rectifier 13, auxiliary cathode amperometric 14 and total current detector 15, secondary one end of constant current circuit transformer 10 is connected with an input terminus of constant current circuit rectifier 13 by after current control loop 11, the secondary the other end of constant current circuit transformer 10 is connected with another input terminus of constant current circuit rectifier 13, the cathode output end of constant current circuit rectifier 13 auxiliary cathode amperometric 14 of connecting successively is connected with described combined type iron anode 5 with (e end) after total current detector 15, the cathode output end (d end) of constant current circuit rectifier 13 is connected with described auxiliary cathode 4, the current output terminal of current control loop 11 is connected with the input terminus of constant current controlling circuit 12, and two output terminals of constant current controlling circuit 12 are connected with the two ends of total current detector 15 respectively.
This constant potential impressed current cathodic protection loop 72 comprises potentiostatic circuit transformer 19, potentiostatic circuit rectifier 16, potentiostatic deposition amperometric 17 and constant potential pilot circuit 18, potentiostatic circuit transformer 19 level two ends are connected with two input terminuss of potentiostatic circuit rectifier 16 respectively, the cathode output end of potentiostatic circuit rectifier 16 is connected with the input terminus of potentiostatic deposition amperometric 17 and constant potential pilot circuit 18, the output terminal of potentiostatic deposition amperometric 17 is connected with the input terminus of described total current detector 15, two output terminals (b end and c end) of constant potential pilot circuit 18 are connected with described shell 1 and reference electrode 8 respectively, the cathode output end (a end) of potentiostatic circuit rectifier 16 is connected with condenser hydroecium or tube sheet.
Constant-current electrolysis loop 71 provides electric current needed for electrolytic iron ion film forming, and constant potential loop maintains electric current needed for suitable protection potential.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, is used for the mild steel anode 52 of electrolysis combined type iron anode 5(periphery specially) make it produce iron ion.The positive pole in constant potential impressed current cathodic protection loop 72 is connected with the positive pole (contact between auxiliary cathode amperometric 14 with total current detector 15) of constant-current electrolysis loop 71 output terminal; by being connected with combined type iron anode 5 again after total current detector 15; negative pole a is connected with hydroecium wall (shell 1), for making the cathodic polarization of hydroecium inwall to required protection potential value.Namely the total current i flowed out by combined type iron anode 5
3the overwhelming majority (i
1) flow to auxiliary cathode 4, be used for electrolysis combined type iron anode 5(mild steel anode 52 specially) make it produce iron ion, portion of electrical current (i
2) flow to hydroecium and tube sheet 2 by the insoluble Magnetic Iron Oxide Anode 51 of combined type iron anode 5 inside, galvanic protection effect is provided.
Principle of work of the present invention is:
Reference electrode 8 is fixed on tube sheet surface or hydroecium wall near it, is used for the protection potential of detection and control hydroecium.
Detect the current potential of protected body (condenser) with reference electrode 8, control outward current with control device 7.In the apparatus, by the protection potential detected with reference electrode 8, automatically control to remain on predetermined current potential, reach best electro-chemical protection.Meanwhile, by the protection potential detected with reference electrode 8, automatically control electric current and keep predetermined value, the iron concentration that dissolving is produced keeps constant, so do not need complicated operation, can extend the life-span of condenser pipe significantly.As previously discussed, structure is simple, the extraordinary external current protection device of processing ease, protected effect to adopt the present invention to obtain, and reaches the industrial protected effect being conducive to wide popularization and application.
The present invention's invention is used for the corrosion prevention of power plant or boats and ships condenser.By external current protection device, electrolytic iron anode, protected body negative electrode, separately establish auxiliary cathode, detect the reference electrode of protected bulk potential, connect these electrodes and protected body is double does power supply and make the current potential of protected body constant and protective current and auxiliary cathode electric current sum are controlled formed at the constant potential continuous current device of steady state value; simple to operate, the effect of electro-chemical protection effect and the protection of electrolytic iron ion can be obtained simultaneously.Adopt iron alloy anode impressed current cathodic protection method and electrolytic iron anode film forming Combined Protection in the present invention; then can solve respective separately protected existing all problems completely; not only give full play to respective advantage, and both has the advantage conforming to and coordinate.
The present invention is based on above-mentioned viewpoint, research and development be used for condenser to impressed current electrochemical protection and utilize the protection of iron ion and, simple, the processing ease of one-piece construction, and the composite electrochemical protector that real work is effective.Obtain following result:
(1) in order to reach best protection effect, adopting and automatically can control the protective current of protective and the current potential of protected body be remained on the continuous current constant potential automatic control type protector of predetermined potential.
(2) at this automatic control type protector except protected body separately arranges negative electrode as except negative electrode; protected electric current and the electric current sum flowing into auxiliary cathode are kept constant; then can guarantee the iron ion of constant basis, and regulate as required, can control simply iron ion amount.
(3) only use the electric current (10-15A) of general impressed current cathodic protection, the iron ion of full concentration can not be obtained.
(4) the present invention makes based on above-mentioned conclusion; it is characterized in that: by impressed current catholic protection device, iron electrode, protected body negative electrode, separately establish auxiliary cathode, detect the reference electrode of protected bulk potential, connect these electrodes and protected body is double does power supply and make the current potential of protected body constant and protective current and auxiliary cathode electric current sum are controlled formed at the constant potential continuous current device of steady state value; operation is very simple, can obtain the effect of impressed current cathodic protection effect and the protection of electrolytic iron ion film forming simultaneously.
Described control device 7 adopts existing hyperchannel potentiostat (such as: Biologic VWP3), can realize constant potential constant current circuit simultaneously and automatically control.
Claims (7)
1. the composite electrochemical device for the protection of prolong series cathode, comprise condenser, this condenser comprises shell, tube sheet and cooling tube, the tube sheet of copper alloy material is arranged in the shell of mild steel material, the cooling tube of copper alloy material is housed in each hole of tube sheet, hydroecium is formed between tube sheet and the blind end of shell, rubber lining is provided with in the inner side of hydroecium, it is characterized in that, combined type iron anode is provided with at the blind end of described shell, insulcrete is provided with in the relative both sides of combined type iron anode, the insulcrete of side is arranged on inside the blind end of shell, outside the insulcrete of opposite side, auxiliary cathode is housed, one is equipped with for detecting the reference electrode of 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 terminal of control device respectively.
2. the composite electrochemical device for the protection of prolong series cathode according to claim 1; it is characterized in that; described combined type iron anode is formed by insoluble Magnetic Iron Oxide Anode and mild steel anode combination, and mild steel annulus anode jacket is at the periphery of insoluble Magnetic Iron Oxide Anode.
3. the composite electrochemical device for the protection of prolong series cathode according to claim 1, it is characterized in that, described combined type iron anode is cylindrical, and its two ends are provided with described insulcrete; At the mild steel annulus anode described in the periphery suit of columniform insoluble Magnetic Iron Oxide Anode.
4. the composite electrochemical device for the protection of prolong series cathode according to claim 1, is characterized in that, described mild steel annulus anode is superposed by multiple mild steel annulus and is enclosed within martial ethiops rod anode, and interfixes with bolt and nut.
5. the composite electrochemical device for the protection of prolong series cathode according to claim 1; it is characterized in that; 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 galvanic protection, and constant-current electrolysis loop is used for producing enough iron ions makes copper alloy surface form rich iron protective membrane.
6. the composite electrochemical device for the protection of prolong series cathode according to claim 5, it is characterized in that, described constant-current electrolysis loop comprises constant current circuit transformer, current control loop, constant current controlling circuit, constant current circuit rectifier, auxiliary cathode amperometric and total current detector, secondary one end of constant current circuit transformer is connected with an input terminus of constant current circuit rectifier by after current control loop, the secondary the other end of constant current circuit transformer is connected with another input terminus of constant current circuit rectifier, the cathode output end of constant current circuit rectifier auxiliary cathode amperometric of connecting successively is connected with described combined type iron anode pole with after total current detector, the cathode output end of constant current circuit rectifier is connected with described auxiliary cathode, the current output terminal of current control loop is connected with the input terminus of constant current controlling circuit, and two output terminals of constant current controlling circuit are connected with the two ends of total current detector respectively,
Described constant potential impressed current cathodic protection loop comprises potentiostatic circuit transformer, potentiostatic circuit rectifier, potentiostatic deposition amperometric and constant potential pilot circuit, potentiostatic circuit transformer secondary output two ends are connected with two input terminuss of potentiostatic circuit rectifier respectively, the cathode output end of potentiostatic circuit rectifier is connected with the input terminus of potentiostatic deposition amperometric and constant potential pilot circuit, the output terminal of potentiostatic deposition amperometric is connected with the input terminus of described total current detector, two output terminals of constant potential pilot circuit are connected with described shell and reference electrode respectively, the cathode output end of potentiostatic circuit rectifier is connected with shell.
7. the composite electrochemical device for the protection of prolong series cathode according to claim 1, is characterized in that, described control device adopts hyperchannel potentiostat.
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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 CN104532259B (en) | 2017-10-20 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106990742A (en) * | 2017-06-02 | 2017-07-28 | 天津隆顺技术服务有限公司 | Opposite potential method anti-corrosion protection linkage control device and system |
| CN109706457A (en) * | 2017-10-26 | 2019-05-03 | 江苏启能新能源材料有限公司 | A kind of the electron anode protection erosion protection system and method for phase-transition heat-storage equipment |
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