CN101492821A - Anticorrosion method employing metallic oxide anode - Google Patents
Anticorrosion method employing metallic oxide anode Download PDFInfo
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- CN101492821A CN101492821A CN 200910014508 CN200910014508A CN101492821A CN 101492821 A CN101492821 A CN 101492821A CN 200910014508 CN200910014508 CN 200910014508 CN 200910014508 A CN200910014508 A CN 200910014508A CN 101492821 A CN101492821 A CN 101492821A
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Abstract
The invention relates to an impressed current cathodic protection corrosion prevention method which adopts a metal oxide anode and is applicable to corrosion prevention of a steel pontoon, a floating dock, a wharfboat and other marine fixed meal structure, belonging to the technical field of electrochemical protection. An impressed current cathodic protection system adopted by the method comprises direct current supply equipment, a tubular metal oxide anode component and a reference electrode component, wherein the direct current supply equipment is arranged on the floating dock metal structure; the tubular metal oxide anode component adopts a hanging metal oxide anode component, and is arranged into the sea; and the reference electrode component is arranged on a fixable position on the floating dock metal structure in hanging manner or fixed manner. The method has the advantages of easy installation, simple operation, long service life, good corrosion prevention effect and strong reliability.
Description
Technical field:
The present invention relates to a kind of impressed current cathodic protection anti-corrosion method that adopts metal oxide anode; be applicable to the corrosion of marine fixed metallic structures such as preventing steel wharfboat, pontoon dry dock, landing stage; be particularly suited for the protection against corrosion of old steel facility, belong to the electro-chemical protection technical field.
Background technology:
At present, galvanic protection and coating combine and can prevent the corrosion of metallic structures in seawater effectively.According to the mode difference that protective current is provided, galvanic protection can be divided into sacrificial anode and two kinds of methods of impressed current.Sacrificial anode protection is by electronegative anode material is connected with hull, by couple action himself dissolving is consumed and produce cathodic protection current, be characterized in simple, reliable, but single anodic generation electric current is less, for obtaining protection fully and long work-ing life, sufficient amount and larger-size sacrificial anode must be installed; Provide required protective current and the impressed current cathodic protection method is a direct supply by the outside, partly constitute by power unit, supplementary anode and reference electrode etc. usually.Be characterized in that driving voltage height, outward current are big, the protection life-span is long, and the size that can regulate outward current automatically with the variation of outer work condition condition, make protected metallic structures be in best guard mode always, but this system complexity comparatively.Although two kinds of methods all can obtain the excellent protection effect, in actual engineering, need to select according to concrete working condition.For marine fixed metallic structures such as the steel wharfboat of newly making, pontoon dry dock, landing stages; in most cases all be to adopt sacrificial protection, this is because sacrificial anode method simple installation need not be safeguarded; for the stationary structure thing, also can design the long protection life-span.Yet, sacrificial anode in the process of work constantly dissolving consume, when its remaining quantity not sufficient when keeping to the enough protection of steel structure, must in time change.Change sacrificial anode and will carry out in dry-docking usually, this need be dragged to works such as wharfboat the place under repair of shipyard ability, and this has not only increased repair expense, and causes the loss that stops production.Therefore, how under the situation that does not influence the normal use of works original cathodic protection system being upgraded is the problem that needs solve.Common a kind of method is to adopt the suspension type sacrificial anode that the body structure surface that is immersed in the seawater is protected at present; but for old works; because the aging badly broken of original paint coating; then must hang a lot of sacrificial anodes and could satisfy the protection needs; and because the protection domain of sacrificial anode is less; when the size of works such as wharfboat is big, its bottom especially central part often be difficult to obtain fully, protection uniformly.
Document [Jack G.Davis; cathodic protection for immersedsurfaces on museum aircraft carrier U.S.S.Lexington; Materials Performance; 1994; No.4; 12-14] in introduced a kind of impressed current cathodic protection system, can effectively protect the old works of this class.What it adopted is anode groundbed technology far away, promptly from the metallic structures that will protect seabed far away the supplementary anode groundbed is being installed, and power unit is installed on the works such as wharfboat.But this method needs the frogman to install under water, and inconvenience is installed, and the works between anode groundbed and wharfboat is had the danger that produces stray current corrosion.U.S. Pat Patent 4,292, and 149 also disclose a kind of supplementary anode assembly that is used to protect offshore oil drilling well facility sea water immersion surface, and it is platinum titanium or platinum niobium composite filament are wrapped on the rope of support and constitute.Although platinum titanium or platinum niobium wire anode have good electrochemical in seawater, the platinum composite anode is owing to complicated process of preparation, so price is expensive, compares economical inadequately with other anode material.Simultaneously, because platinum titanium or platinum niobium composite filament are directly to be wrapped on the rope of support, corrosive mediums such as the chlorine that produces during anode working are easy to cause the aging or damaged of support cable.In addition, the cable splice that exists between platinum titanium or platinum niobium composite filament and the tie cable damages easily, easily causes whole protecting thrashing.
Summary of the invention:
The objective of the invention is to overcome the shortcoming that exists in the prior art; seek to design a kind of anti-corrosion method that adopts the impressed current cathodic protection of suspension type metal oxide anode; this method is easy for installation; the protection life-span is long; protect effective; can work stably in a long term, and can not disturb near metal construction deposits yields stray current other.
To achieve these goals, after the present invention selects impressed current cathodic protection system and tubular metal oxide anode thereof earlier, assembling also is fixedly connected on protected metallic structures or the wharfboat, connect power supply and carry out anti-corrosion protection, the impressed current cathodic protection system that is adopted comprises DC power supply device, tubular metal oxide anode assembly and reference electrode assembly; DC power supply device is arranged on the metallic structures of wharfboat, to reduce the length of coupled anode cable and cathode cable, tubular metal oxide anode assembly adopts the suspension type metal oxide anode assembly, from the steel structure cloth be put into marine, but adopt suspension type to install or the reference electrode assembly of fixed installation is arranged on fixed position on the metallic structures of wharfboat.
DC power supply device of the present invention is input as single-phase or three-phase alternating current, and the positive terminal of direct current output connects anode cable, and negative terminal connects cathode cable; DC power supply device adopts the potentiostat of control automatically or adopts the rectifier of manual regulation; DC power supply device is provided with the reference electrode connection terminal and is connected on the reference electrode assembly, measures the current potential of protected metallic structures.
But reference electrode assembly of the present invention is arranged on the fixed position of wharfboat, and this position is positioned at the centre of two anode assemblies, or away from the position of anode assemblies, the reference electrode body adopts silver/silver chloride, high purity zinc (greater than 99.99%Zn) or zinc alloy; The sheath of reference electrode adopts insulating material such as glass reinforced plastic, nylon, polyvinyl chloride or polyethylene to make, and being shaped on permeable hole or semi-permeable membranes and seawater on the sheath carries out ion-exchange, is used to prevent the damage or the pollution of reference electrode body; Reference electrode assembly by the board suspension type is installed, or is fixed on ship side with reinforcing bar, is immersed in the seawater and is positioned as close to the surface of protected works, the ohmmic drop when reducing to measure.
Tubulose oxide anode assembly of the present invention adopts titanium parent tube shape metal oxide anode body, be covered with the ceramic mixed metal oxide of conduction at the working-surface of anode bodies, oxide compound is by a kind of in a kind of in the platinum group metal oxide such as ruthenium oxide, iridium oxide and palladous oxide or two kinds and above and the non-noble metal oxides such as titanium oxide, stannic oxide, tantalum oxide or two kinds and constitute above the mixing, and the content of metal oxide should be not less than 30% mol ratio; When the content of metal oxide was worth less than this, the chemical property of Mixed Metal Oxide Coated Titanium Anodes is deterioration obviously; Be electrically connected at the middle part of anode assemblies between anode cable and the tubulose oxide anode assembly inwall, adopt the redundant sealing of twice, between tubular metal oxide anode assembly and anode cable, fill the sealing material earlier as Resins, epoxy or paraffin, adopt rubber sealing boot at the two ends of tubular metal oxide anode assembly then, extruding type carries out secondary seal; Many the tubulose metal oxide anodes of on same anode cable, connecting simultaneously; Tubular metal oxide anode assembly assembles the back in advance, and to adopt the mode cloth hang to be put into from the wharfboat marine, and the concrete that the bottom is connected with fixing usefulness is anchor block fixedly; Anode cable adopts special cable, adopts a multi-strand wire rope to support in the middle of it.
Impressed current cathodic protection system of the present invention comprises at least one potentiostat, a tubulose oxide anode and a reference electrode; The quantity of the size of the quantity of potentiostat and rated output voltage, electric current, tubular metal oxide anode and reference electrode is all determined according to size, structural shape and the coating situation of protected metallic structures.
The present invention compared with prior art has following advantage: the one, adopt impressed current cathodic protection, and the protective current that provides is big, and the protection life-span is long, and can make works be in the good protection state always; The 2nd, do not need dry-docking to install, can not influence the normal use of works, be suitable for that old metallic structures is carried out securing system and upgrade; The 3rd, tubulose oxide anode assembly adopts titanium to make anode substrate, and anode is in light weight, has the favorable mechanical performance, is convenient to carrying and installation; Adopted the mixed metal oxide of conduction to make anode coating, made this anode have high stability and very low rate of consumption, thereby can have long work-ing life; Because oxide coating has high electrochemical activity, can adopt bigger working current density and lower electric power output voltage, thereby have higher efficient, and price is cheap than platinum anode, can save the precious metal resource; The 4th, adopted serial type tubulose oxide anode structure, can increase the spacing between anode quantity and the adjusting anode easily; The 5th, this metal oxide anode assembly is to assemble in advance in factory, and has adopted redundant sealed structure at the cable splice place, has improved the reliability of whole anode assemblies; The 6th, adopted nearly anode system, therefore can near other metal construction deposits yields stray current not disturbed.
Description of drawings:
Fig. 1 is that the invention process is in the etch-proof structural principle synoptic diagram of the wharfboat of metal construction object, comprising wharfboat 1, DC power supply device 2, anode cable 3, cathode cable 4, reference electrode assembly 5, tubulose oxide anode assembly 6 and fixing anchor block 7.
Embodiment:
Also the present invention will be further described in conjunction with the accompanying drawings below by specific embodiment.
Present embodiment is immersed in position in the seawater in order to protect wharfboat 1 works such as grade, adopt the impressed current cathodic protection method, DC power supply device 2 is arranged on the works wharfboat 1, be input as single-phase or three-phase alternating current, the positive terminal of direct current output connects supplementary anode cable 3, and negative terminal connects cathode cable 4; Power unit adopts the potentiostat of control automatically or the rectifier of manual regulation, and DC power supply device 2 is provided with the reference electrode connection terminal and is connected on the reference electrode assembly 5, measures the current potential of protected metallic structures; Reference electrode assembly 5 is arranged in representational fixed position on 1 works of wharfboat, the position is positioned at the centre of two anode assemblies 6, or from anode assemblies 6 position far away of trying one's best, promptly when this position reached protective potential range, whole metallic structures had all obtained excellent protection; Reference electrode assembly 5 is made up of reference electrode body and sheath, and the reference electrode body adopts silver/silver chloride, high purity zinc (greater than 99.99%Zn) or zinc alloy, and they have good electrode stability in seawater; Sheath adopts insulating material such as glass reinforced plastic, nylon, polyvinyl chloride or polyethylene to make, and being shaped on permeable hole or semi-permeable membranes and seawater on it carries out ion-exchange, is used to prevent the damage or the pollution of reference electrode body; Reference electrode assembly 5 in the wharfboat 1 outboard suspension type install or be fixed on ship side with reinforcing bar, be immersed in the seawater, and be positioned as close to the surface of protected works, the ohmmic drop when reducing to measure.
The tubular metal oxide anode assembly 6 of present embodiment adopts titanium parent tube shape metal oxide anode body, in light weight, be convenient to install and have enough physical strengths, be covered with the ceramic mixed metal oxide of conduction at the working-surface of anode bodies, mainly by a kind of in a kind of in the platinum group metal oxide such as ruthenium oxide, iridium oxide or palladous oxide or two kinds and above and the non-noble metal oxides such as titanium oxide, stannic oxide, tantalum oxide or two kinds and above constitute, and the content of metal oxide containing precious metals should be not less than 30% (mol ratio); When the content of metal oxide containing precious metals was worth less than this, the chemical property of Mixed Metal Oxide Coated Titanium Anodes is deterioration obviously; Because mixed metal oxide coating has good electrical conductivity, big specific surface area and high chemistry, electrochemical stability, therefore the titanium-based metal oxide anode has than higher electro catalytic activity of platinum anode and littler rate of consumption, be a kind of high performance auxiliary anode material, its price is also low than platinum anode simultaneously; Electrically connect the middle part that is positioned at the sheath body between anode cable 3 and the sheath body inwall, can effectively reduce the termination effect that supplementary anode exists, make the distribution of current of anode body surface more even, thereby prolong the anodic life-span; For improving the reliability of anode jointing, adopted the redundant sealing of twice, promptly between sheath body and anode cable 3, fill the sealing material earlier as Resins, epoxy or paraffin, adopt rubber sealing boot at the two ends of sheath body then, mode by extruding is carried out secondary seal, when an anodic discharge capacity not enough, or in order to improve distribution of current longitudinally, many the tubulose metal oxide anodes of on same anode cable, connecting simultaneously, tubular metal oxide anode assembly assembles in advance in factory, both improve the reliability of whole anode assemblies, also made things convenient for site operation; 1 steel structure adopts the mode cloth of hanging to be put into marine to anode assemblies 6 from the wharfboat, the concrete that its underpart is connected with fixing usefulness is anchor block 7 fixedly, for preventing anode cable 3 stressed damages, adopt special cable, adopt a multi-strand wire rope to play enhancement therebetween.The cathodic protection system of present embodiment comprises at least one potentiostat, an anode and a reference electrode, and the concrete quantity fibrous root of the quantity of potentiostat and the size of rated output voltage/electric current, supplementary anode and reference electrode is determined according to size, structural shape and the coating situation of protected metallic structures.
Embodiment:
Present embodiment is chosen certain shipyard one large-scale wharfboat 1, once adopts sacrificial protection, because sacrificial anode runs out of, has reached design service life, needs to upgrade cathodic protection system.The replacing sacrificial anode owing to can not in time lie up, and wish to obtain the longer protection life-span, the impressed current cathodic protection method adopted; According to the protective current amount of design, adopted the potentiostat of a specified 160A/16V of being output as to make direct supply, its positive pole links to each other with anode, and negative pole is received on the steel wharfboat 1; 4 suspension type tubulose titanium base Mixed Metal Oxide Coated Titanium Anodes assemblies 6 have been adopted, be connected with a sheath on every anode assemblies, anode bodies is of a size of Φ 25mm * 1000mm, the special-purpose anode cable 3 of wireline enhanced is arranged in the middle of adopting, can bear the tensile effect of hanging, the anode bottom hangs with fixedly anchor block 7 of the heavy concrete of 20kg; Every specified discharge capacity of anodic is about 40A, and be 15 years life; Four anodes are arranged in two topsides, two of every sides, uniform distribution; Adopt two silver/silver chloride reference electrodes, a side that is arranged in wharfboat 1, the position between two anodes; Another is arranged in and does not hang the anodic side; The former is used to potentiostat that supervisory signal is provided, and the latter is used to measure the protection potential of wharfboat 1; After the cathodic protection system operation, adopt mounted reference electrode and portable reference electrode that protection potential is detected, the result show wharfboat 1 immersion protection potential everywhere all be positioned at-0.8V～-1.0V, show that hull has been in the good protection state; Potentiostat, reference electrode and anode assemblies stable work in work can satisfy the requirement of wharfboat corrosionproof protection.
Claims (4)
1, a kind of anti-corrosion method that adopts metal oxide anode, after it is characterized in that selecting impressed current cathodic protection system and tubular metal oxide anode thereof, assembling also is fixedly connected on protected metallic structures or the wharfboat, connect power supply and carry out anti-corrosion protection, the impressed current cathodic protection system that is adopted comprises DC power supply device, tubular metal oxide anode assembly and reference electrode assembly; DC power supply device is arranged on the metallic structures of wharfboat, tubular metal oxide anode assembly adopts the suspension type metal oxide anode assembly, from the steel structure cloth be put into marine, but adopt suspension type to install or the reference electrode assembly of fixed installation is arranged on fixed position on the metallic structures of wharfboat.
2, the anti-corrosion method of employing metal oxide anode according to claim 1 is characterized in that DC power supply device is input as single-phase or three-phase alternating current, and the positive terminal of direct current output connects anode cable, and negative terminal connects cathode cable; DC power supply device adopts the potentiostat of control automatically or the rectifier of manual regulation; DC power supply device is provided with the reference electrode connection terminal and is connected on the reference electrode assembly, measures the current potential of protected metallic structures.
3, the anti-corrosion method of employing metal oxide anode according to claim 1 is characterized in that position that the reference electrode assembly is arranged on the wharfboat is positioned at the centre of two anode assemblies, or away from the position of anode assemblies; The reference electrode body adopts silver/silver chloride, purity greater than 99.99% zinc or zinc alloy; The reference electrode sheath adopts glass reinforced plastic, nylon, polyvinyl chloride or polythene material to make, and is shaped on permeable hole or semi-permeable membranes and seawater on the sheath and carries out ion-exchange; Reference electrode assembly by the board suspension type is installed, or is fixed on ship side with reinforcing bar, is immersed in the seawater and the surface of close protected works.
4, the anti-corrosion method of employing metal oxide anode according to claim 1, it is characterized in that tubulose oxide anode assembly adopts titanium parent tube shape metal oxide anode body, be covered with the ceramic mixed metal oxide of conduction at the working-surface of anode bodies, oxide compound is by a kind of in a kind of in ruthenium oxide, iridium oxide or the palladous oxide or two kinds and above and titanium oxide, stannic oxide or the tantalum oxide or two kinds and constitute above the mixing, and the content of metal oxide is not less than 30% mol ratio; Be electrically connected at the middle part of anode assemblies between anode cable and the tubulose oxide anode assembly inwall, adopt the redundant sealing of twice, filling epoxy resin or paraffin between tubulose oxide anode assembly and anode cable adopt the rubber sealing boot extruding type to carry out secondary seal at the two ends of tubulose oxide anode assembly then earlier; Many the tubulose metal oxide anodes of on same anode cable, connecting simultaneously; Tubular metal oxide anode assembly assembles back suspension type from the wharfboat in advance and lays marinely, and the concrete that the bottom is connected with fixing usefulness is anchor block fixedly; Adopt a multi-strand wire rope to support in the middle of the anode cable.
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Cited By (13)
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| CN101928945A (en) * | 2010-08-24 | 2010-12-29 | 中国船舶重工集团公司第七二五研究所 | Impressed current catholic protection device for ship |
| CN102312240A (en) * | 2010-06-29 | 2012-01-11 | 中国石油天然气股份有限公司 | Simulate optimizing device for stray current interference corrosion |
| CN102500533A (en) * | 2011-11-03 | 2012-06-20 | 昆明理工大学 | Method for coating corrosion-resistant paint on surface of steel |
| CN102677065A (en) * | 2012-05-22 | 2012-09-19 | 广东明阳风电产业集团有限公司 | Offshore wind turbine with impressed current cathode anti-corrosion protection and monitoring device |
| CN103205754A (en) * | 2012-01-12 | 2013-07-17 | 上海船研环保技术有限公司 | Buoyant suspension type impressed current cathodic protection device |
| CN103590334A (en) * | 2012-08-15 | 2014-02-19 | 深圳市市政设计研究院有限公司 | Stay rope structure having corrosion preventing function and corrosion preventing protection method of stay rope |
| CN103602993A (en) * | 2013-11-26 | 2014-02-26 | 中国人民解放军92537部队 | Protective spacer bush of iron alloy sacrificial anode for seawater pipeline |
| CN109023384A (en) * | 2017-06-09 | 2018-12-18 | 四川启昌管道工程有限责任公司 | A kind of novel convenient moveable cathodic protection skid mounted equipment |
| CN110079810A (en) * | 2019-06-11 | 2019-08-02 | 四川德源石油天然气工程有限公司 | A kind of device and replacing options being conveniently replaceable underwater impressed current anode |
| CN110508609A (en) * | 2019-08-12 | 2019-11-29 | 浙江省有色金属地质勘查局 | A kind of heavy metal-polluted soil improvement anode construction and heavy metal-polluted soil processing unit |
| CN112342550A (en) * | 2020-09-22 | 2021-02-09 | 大唐可再生能源试验研究院有限公司 | Fan tower barrel rust removal method |
| CN113814145A (en) * | 2021-09-07 | 2021-12-21 | 长江三峡通航管理局 | Ship lock herringbone door metal structure anticorrosion treatment process |
| CN114351152A (en) * | 2021-12-07 | 2022-04-15 | 海洋石油工程股份有限公司 | String-shaped sacrificial anode applied to marine steel structure |
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2009
- 2009-02-26 CN CN2009100145086A patent/CN101492821B/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102312240A (en) * | 2010-06-29 | 2012-01-11 | 中国石油天然气股份有限公司 | Simulate optimizing device for stray current interference corrosion |
| CN102312240B (en) * | 2010-06-29 | 2013-04-24 | 中国石油天然气股份有限公司 | Simulation optimizing device for stray current interference corrosion |
| CN101928945B (en) * | 2010-08-24 | 2012-05-30 | 中国船舶重工集团公司第七二五研究所 | Impressed current catholic protection device for ship |
| CN101928945A (en) * | 2010-08-24 | 2010-12-29 | 中国船舶重工集团公司第七二五研究所 | Impressed current catholic protection device for ship |
| CN102500533A (en) * | 2011-11-03 | 2012-06-20 | 昆明理工大学 | Method for coating corrosion-resistant paint on surface of steel |
| CN102500533B (en) * | 2011-11-03 | 2014-07-02 | 昆明理工大学 | Method for coating corrosion-resistant paint on surface of steel |
| CN103205754A (en) * | 2012-01-12 | 2013-07-17 | 上海船研环保技术有限公司 | Buoyant suspension type impressed current cathodic protection device |
| CN102677065A (en) * | 2012-05-22 | 2012-09-19 | 广东明阳风电产业集团有限公司 | Offshore wind turbine with impressed current cathode anti-corrosion protection and monitoring device |
| CN103590334B (en) * | 2012-08-15 | 2016-05-04 | 深圳市市政设计研究院有限公司 | A kind of anti-corrosion protection method of stayed structure and the drag-line with anti-corrosion function |
| CN103590334A (en) * | 2012-08-15 | 2014-02-19 | 深圳市市政设计研究院有限公司 | Stay rope structure having corrosion preventing function and corrosion preventing protection method of stay rope |
| CN103602993A (en) * | 2013-11-26 | 2014-02-26 | 中国人民解放军92537部队 | Protective spacer bush of iron alloy sacrificial anode for seawater pipeline |
| CN109023384A (en) * | 2017-06-09 | 2018-12-18 | 四川启昌管道工程有限责任公司 | A kind of novel convenient moveable cathodic protection skid mounted equipment |
| CN110079810A (en) * | 2019-06-11 | 2019-08-02 | 四川德源石油天然气工程有限公司 | A kind of device and replacing options being conveniently replaceable underwater impressed current anode |
| CN110079810B (en) * | 2019-06-11 | 2021-05-04 | 四川德源石油天然气工程有限公司 | Device convenient for replacing underwater auxiliary anode and replacing method |
| CN110508609A (en) * | 2019-08-12 | 2019-11-29 | 浙江省有色金属地质勘查局 | A kind of heavy metal-polluted soil improvement anode construction and heavy metal-polluted soil processing unit |
| CN112342550A (en) * | 2020-09-22 | 2021-02-09 | 大唐可再生能源试验研究院有限公司 | Fan tower barrel rust removal method |
| CN113814145A (en) * | 2021-09-07 | 2021-12-21 | 长江三峡通航管理局 | Ship lock herringbone door metal structure anticorrosion treatment process |
| CN114351152A (en) * | 2021-12-07 | 2022-04-15 | 海洋石油工程股份有限公司 | String-shaped sacrificial anode applied to marine steel structure |
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Granted publication date: 20110112 Termination date: 20130226 |