CN1003525B - Overhead metallic pipe cathode protector - Google Patents
Overhead metallic pipe cathode protector Download PDFInfo
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- CN1003525B CN1003525B CN86100581.3A CN86100581A CN1003525B CN 1003525 B CN1003525 B CN 1003525B CN 86100581 A CN86100581 A CN 86100581A CN 1003525 B CN1003525 B CN 1003525B
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Abstract
The present invention relates to a cathode protector of an overhead metal pipeline, which comprises a protecting structure (a metal pipeline to be protected is used as a cathode, a solid electrolyte coating is used as a continuous phase, and an electronic conducting coating is used as an auxiliary electrode), a protecting potential measuring system (comprising a graphite solid reference electrode, an impedance converter and a digital voltmeter) and a DC power supply system (potentiostat). After a power supply is switched on, a metal cathode to be protected is polarized to a certain value by the overhead metal pipeline by the aid of the solid electrolyte coating depending on an external current so as to suppress corrosion. The cathode protector is suitable for various overhead metal pipelines, metal containers and metal components of large railway bridges and offshore platform splashing zones exposed to gas phase environment.
Description
Involved in the present invention is a kind of electrochemical metal erosion protection system.Particularly need only apply one deck solid electrolyte coating in the metallic surface; form solid electrolyte layer); and coating one deck electronic conduction auxiliary anode material (formation anode layer) applies a direct current power supply between protected metal (being negative electrode) and anode *; after adding certain cathodic current; cathodic polarization can make it obtain reliable galvanic protection to a certain degree.This kind device is applicable to the galvanic protection of overhead metal pipe.
Existing cathode protection technology has prolonged has used century more than one, becomes a cover and is internationally recognized more sophisticated cathode protection technology.Be widely used in the protection of hardwares such as underwater metal component, underground oil transportation (gas) pipeline, underground cable, underground metal tank.The principle of this technology is: being in protected metal in the external phase ionogen (soil, seawater) as negative electrode, set up supplementary anode, after the energising, protected metallic cathode is polarised to a certain degree slow down or suppresses a kind of cathode protection technology of corrosive.But; this technology has following shortcoming: in (1) its cathodic protection system; anode surface area is much smaller than cathodic surface area; promptly just can protect the cathodic metal body of big area scope with less annode area; also just therefore, it is inhomogeneous that anode flows to the distribution of current of negative electrode, exists potential gradient at the cathode surface current potential and distribute; under certain condition, anode far away (or disperseing anode) can reduce this gradient difference (minimum (or the highest) current potential is all in the scope of safeguard protection current potential when making this gradient difference.); Also can cause simultaneously cathodic protection current to flow to the hardware of contiguous (non-protective), make it run into galvanic corrosion, cathodic protection current runs off and also can influence the enforcement of former cathode protection technology when serious.(2) in addition, need set up isolated flange, electrical isolation is carried out in protective belt and non-protection area in some occasion; to improve the protection effect, (3) be the more important thing is and can not be protected (the clear 48-10439 1973,4 of Japanese Patent to the hardware that is in the gaseous environment; 3, and United States Patent (USP) 2847375,1958; 8,12, (international petroleum engineering conference collection of thesis four; 1982; 3, supE 9986, and supE 9983).
There is a large amount of hardwares to expose in atmosphere in the world.Because these metallic surfaces are air dielectrics, perhaps, though there is the thin ionogen of one deck (as rain heavily or dewfall etc.) on its surface, because of ionogen can not form external phase, so, become the forbidden zone of domestic and international galvanic protection always.
Purpose of the present invention; be to provide a kind of new cathodic protector; be about to the metallic surface artificial one deck external phase solid electrolyte coating in the atmospheric environment; make supplementary anode with the equadag coating that conductivity is good; and with special potentiostat; as reliable and stable polarization power supply; (the former is as measuring basis for the protection potential measuring system that employing is made up of graphite reference electrode and impedance transformer, digital voltmeter (DVM); the latter guarantees the error measured), make this metalloid member obtain galvanic protection.Elimination is to the interference of contiguous non-protection area, do not need to adopt corresponding anti-interference method that stable, easy, high-quality, galvanic protection reliably can be provided.
The inventive system comprises: protection structure, electric supply system and protection potential measuring system three major parts.
1. the protection structure has three layers:
The built on stilts hardware of internal layer-desire protection is made negative electrode;
Middle level-solid electrolyte coating is done external phase, is coated in metal component surface, subsequently, solid reference electrode is bonded on the coating securely, and the part beyond the butt joint interface, encapsulate with insulating material;
The supplementary anode coating of skin-coating one deck electronic conduction is on solid electrolyte coating.
2. power supply system of DC source: adopt special-purpose potentiostat (PS-2 type) that the present invention developed power supply system as power supply.This potentiostat has higher input impedance (〉=10
11Ohm), have from the fluctuation range of nanoampere level to tens ampere level electric current output, the error of constant potential is not more than 10 millivolts.Higher frequency response characteristic is arranged, and (frequency response range is: 10
-3～10
3Conspicuous/second) and multijunction (13) potential monitoring, and protection parameter computerized print recording unit (is promptly regularly gone the rounds the print record instrument, can be write down year, month, day, hour, min, second, received current, voltage, energising point current potential φ simultaneously
0And 13 monitoring point current potential (φ
1-φ
13)).
3. protection potential measuring system: comprise three component parts: (1) solid graphite reference electrode; (2) impedance transformer (comprising lead-in wire); (3) digital current potential table.The protection potential of metallic conduit in solid electrolyte layer measured with the solid reference electrode that is buried in the solid electrolyte.It is a reference electrode of measuring protection potential.Because the electronic conductance of solid electrolyte is lower, directly measuring current potential with low resistance current potential table has very big error.Therefore, used impedance transformer in the potential measurement system, during with electric current≤0.1 of the reference electrode of guaranteeing the measuring error of current potential, make to flow through microampere, the potential drifting of its solid reference electrode is not more than 20 millivolts; Guarantee that potential drifting also is not more than 20 millivolts when far range is measured current potential.These characteristics make PS-2 type potentiostat can monitor the protection potential of 13 points simultaneously.
Protected metallic conduit joins as the negative pole of negative electrode and direct supply; Supplementary anode and positive source join.
After circuit was connected, impressed current flowed to solid electrolyte from positive source through supplementary anode, flows through protected metallic conduit and gets back to power cathode from solid electrolyte again.When protected metallic conduit in solid electrolyte cathodic polarization to a certain degree (during the anode take-off potential of corrosion cell, corrosion just is suppressed, and has promptly realized galvanic protection.
Effect of the present invention is as follows:
To saving steel, save the consumption of human and material resources and financial resources, effect is remarkable.
There is 80% metal exposed in the whole world in atmospheric environment; Chemical system has 70% pipeline, and is long apart from 2% exposed tube being arranged in the transition pipeline in atmosphere.
If 2% of these metallic conduits are pressed technology implementation galvanic protection of the present invention, prolongs life is one times at least.Can save oil, chemical industry and be used to 8000 tons of the iron and steel that keep in repair and change every year.By 2000 gross annual output values is that 28,000 hundred million its losses are 2% calculating, and it can save 11.2 hundred million yuan of Renminbi.180,000 tons of iron and steel can be saved in the whole nation.The indirect losses that accident caused such as the fire that causes because of the corrosion failure of oil pipeline, blast are then more considerable.Use technology of the present invention, tremendous loss can be avoided fully like this.
The present invention is rational in infrastructure, and is easy to operate.Except that the overhead metal pipe that is applicable to atmospheric environment PetroChina Company Limited., chemical industry, also be applicable to the marine metal member of the ocean platform splash zone in the marine atmosphere, Large-scale Railway bridge, metal vessel (except the two property metals) etc.They promptly are the negative electrode-desire protective money metal elements of the interior indication of protection structure in the content of the present invention.
Below in conjunction with accompanying drawing, introduce performance of the present invention in detail.
1. the making of protection structure:
Fig. 1 is the cathode protection technology schematic diagram of overhead metal pipe,
(1)-polarization power supply among the figure
(2)-plate lead
(3)-electronic conduction supplementary anode layer (materials such as graphite or graphite rolled-up stock, magnesium, aluminium, zinc)
(4)-solid electrolyte coating
（CK-Ⅰ，CK-Ⅱ，CK-Ⅲ，CK-Ⅳ）
(5)-protected metallic conduit (negative electrode)
(6)-cathode leg
The flow direction of (→)-impressed current
Metallic conduit, solid electrolyte coating and electronic conductive coating (supplementary anode layer) by the desire protection constitute the protection structure.
Solid electrolyte coating is with spraying or draw together and technology such as be coated with and directly be coated in metalwork surface through rust cleaning and cleaning, before the curing, solid reference electrode is imbedded in the coating, draw lead-in wire, promptly form one deck in conjunction with firm, corrosion resistant solid electrolyte coating after the curing,, the surface that technology is coated in solid electrolyte coating such as be coated with spraying, drawing together again with electronic conduction coating at pipe surface, after the curing, form the good supplementary anode layer of one deck conductivity.
2. the enforcement of protecting cathode of overhead metal pipe technology
Fig. 2 is galvanic protection device for carrying out said figure.
(1)-DC power supply equipment (polarization power supply) among the figure
(2 ')-positive contact
(3)-supplementary anode layer (anode)
(4)-solid electrolyte coating
(5)-overhead metal pipe (negative electrode)
(6 ')-negative contact
(7)-solid reference electrode (alloy zinc, graphite or with the metal of protected body material of the same race)
(8)-impedance transformer (the unicircuit voltage follower by positive-negative power supply is formed)
Reference junction on the DC power supply equipment (1) is linked to each other its indirect-impedance transformer (8) with solid reference electrode (7).Anode in positive contact (2 ') on the electronic conduction anode layer (3) and (1) is joined.The electric current that passes through is therebetween measured with reometer.The negative contact (6 ') that is positioned on the suspension pipe line (5) is joined with potentiostat the moon joint.In the galvanic protection process, the voltage range that negative and positive two interpolars are applied is 1 volt-30 volts.Electric current is that nanoampere arrives ampere.
The protection potential of negative electrode is measured with the sticking solid reference electrode that applies in solid electrolyte coating.Because the electronic conductance of solid electrolyte is lower, not directly use low resistance (as 1 megaohm) current potential table to measure current potential, in order to avoid produce very big error.Adopted impedance transformer (8) in the present technique, to guarantee the error of potential measurement.Its limit of error is during in the electric current of reference electrode of flowing through≤0.1 microampere, and the potential shift of graphite reference electrode is not more than 20 millivolts.Its protection effect is controlled in skew spontaneous potential 0.7-1.8 volt scope with the best protection current potential.General current potential can be in skew spontaneous potential 0.5-2.5 volt scope, current density nanoampere～milliampere/centimetre
2Scope.
Fig. 3 is a PS-2 type solid electrolyte potentiostat schematic diagram.
CPU MPU among the figure
The PRT printer
The DE digital wash
CAI/O MPU input/output interface
IC
1The unicircuit differential operational amplifier
IC
2The polarizing voltage sampling circuit
IC
3The polarizing current sampling circuit
IC
4Control reference electrode impedance transformer
IC
5Measure the reference electrode impedance transformer
φ
0Control reference potential signal
φ
1-φ
13The reference potential signal is measured in 13 monitoring points
U polarizing voltage signal
I polarizing current signal
The RE graphite reference electrode
The protected body metal-negative electrode of WE
The CE supplementary anode
The E polarization power supply
The RU voltage sampling resistor
The Ri current sampling resistor
The given current potential signal of Ui
Potentiostat is to guarantee that protected body metal can constant important instrument in a certain selection of appointed when galvanic protection.It is to utilize the unicircuit differential operational amplifier through after the comparison operation, makes current potential between reference electrode and the protected body metal, promptly controls reference potential signal φ
0Equal given current potential instruction signal Ui, the former is from the motion tracking latter, and reaches the purpose of constant potential.Simultaneously, by polarizing voltage sampling circuit IC
2, polarizing current sampling circuit IC
3And the impedance transformer IC of voltage follower composition
4, IC
5Polarizing voltage signal U, polarizing current signal I controls reference potential signal φ respectively
*Measurement reference potential signal φ with 13 monitoring points
1-φ
13CAI/O shows on digital watch DE according to sequential by the MPU input/output interface,, sets control printer prints (PRT) simultaneously by MPU CPU according to clock controller.
3. the preparation of solid electrolyte coating and anode layer material
The preparation and the composition proportion of subordinate list 1 solid electrolyte coating.
Preparation of subordinate list 2 anode layer materials and ratio range.
The solid electrolyte powder is β " (β)-aluminum oxide *, phosphorus zirconium silicate, zirconium white
(the existing β of * " aluminum oxide also has beta-alumina)
Mineral binder bond is the environment that water glass glue is applicable to comparatively high temps;
Organic binder bond is epoxy glue, polyurethane adhesive, organic silica gel, (being applicable to the environment of lesser temps); Solidifying agent is T
31, T
*(production of auxiliary reagent factory, Kunshan) Tk-Sodium Silicofluoride, 717-〈 ﹠﹠〉production of a system part three factories)
T
651(651 type polyamide resins, xiangtan, hunan province resin processing plant produces).
The chemical ingredients of binding agent and solidifying agent is as follows
Binding agent:
717-forms single-liquid type by epoxy compounds and isocyanic ester polycondensation, the binding agent of solvent-free ambient temperature curable.
Solidifying agent:
T
31-contain the fatty amine modified compound of phenyl ring, in molecular structure, the reactive hydrogen of existing fatty amine contains again the favorable group of epoxy resin cure energy, belongs to the modified amine compound of the strong hydrophobic nature of a kind of tool;
T
33-the trade mark is TF
1, at T
31Improve on the basis and form low viscosity, erosion resistance is better, does not add the modified amine compound that contains phenyl ring of thinner;
Tk-Sodium Silicofluoride, molecular formula are Na
2SiF
6;
T
651-651 type polyamide resins, it can be to be the dimer of unsaturated fatty acids of raw material and the low-molecular-weight polyamide resin that the diamine condensation forms with the vegetables oil,
The graphite paint composition is: Graphite Powder 99 adding additives 717;
Graphite rolled-up stock, magnesium, aluminium, zinc etc. also can be made the supplementary anode layer material.
According to table 1 and table 2, specify the preparation of solid electrolyte coating and anode layer coating respectively:
A. the preparation of solid electrolyte coating;
A CK-I coating
The galvanic protection occasion of hardware in 0 ℃～80 ℃ general gaseous environment is when the granularity of solid electrolyte powder (S) is＜40 orders 100～160 orders; during＞200 orders; T: S is respectively 1: 8,1: 1.5～1: 8 and 1: the 15(weight ratio), and U: T=15～35%(weight)
Wherein S is β " (β)-aluminum oxide
Binding agent T is an epoxy glue
Solidifying agent U is T
31Or T
651
B.CK-II coating
The suitable environment temperature is 0 ℃～80 ℃
S is phosphorus zirconium silicate or zirconium white, and T is an epoxy glue, when S uses granularity＜40 orders
U T
*When S is＞200 orders or 100-160 order, U T
33
When the S granularity is respectively＜40 orders, 100～160 orders, during＞200 orders, T: S is respectively 1: 7,1: 1.5～1: 6.5,1: 1.
C CK-III coating
When 10 ℃～50 ℃ moist gaseous environments and low temperature (5 ℃), S select for use β ' (β)-aluminum oxide
T goes back organic silica gel or polyurethane adhesive except that epoxy glue, U is T
33
The same CK-1 of the size range of S, T: S and U: T
D.CK-IV coating
When sour environment and 150 ℃～300 ℃ hot environments enforcement galvanic protections, S is β " (β)-aluminum oxide
T is a water glass glue,
U is T,
When the granularity of S is＜40 orders, 100～160 orders, during＞200 orders, T: S is respectively 1: 6,1: 0.8～1: 6,1: 0.8, U: T was 3～10%(weight).
The proportioning of B anode layer coating is:
When Graphite Powder 99 R granularity is＜60 orders, 100～200 orders, during 200 orders, Graphite Powder 99 R and binding agent 717 are than R: 717 is respectively 1: 0.9,1: 0.2～0.8,1: 0.2(weight).
The preparation of table 1 solid electrolyte coating and composition proportion
Annotate: * T in the table
31Auxiliary reagent factory ,-Kunshan produces * Tk Sodium Silicofluoride, commercially available
* T
33-the same * T
651(651 type polyamide resins, xiangtan, hunan province resin processing plant produces).
Preparation of table 2 anode layer material and composition proportion
* 717 binding agent-Shanghai systems part, three factory's products
Claims (45)
1, a kind of cathodic protector of overhead metal pipe is characterized in that being made up of following three parts:
A) protection structure (hardware that comprises the desire protection is done negative electrode, and solid electrolyte coating is done external phase, and electronic conduction supplementary anode layer is done anode, through lead cathode and anode and direct supply is joined);
B) protection potential measuring system (comprise be buried in the solid electrolyte coating and with the solid reference electrode of its secure bond, impedance transformer (comprising lead-in wire) and digital current potential table);
C) power supply system of DC source (potentiostat).
2, cathodic protector according to claim 1 is characterized in that in the described solid electrolyte coating:
A) solid electrolyte powder (S) is:
β " (β)-aluminum oxide, phosphorus zirconium silicate, zirconium white
B) binding agent (T) is:
Water glass glue, epoxy glue, polyurethane adhesive, organic silica gel
C) solidifying agent (U) is:
T
31, T
33(the two is the auxiliary reagent factory, Kunshan and produces) T
K(Sodium Silicofluoride, commercially available),
T
651(651 type polyamide resins, xiangtan, hunan province resin; Produce).
3, cathodic protector according to claim 2 is characterized in that the preparation of solid electrolyte coating is:
A) CK-I coating:
The galvanic protection occasion of hardware in 0 °～80 ℃ general gaseous environments, when the S granularity is＜40 orders, when 100～160 orders and＞200 orders, T: S is respectively:
1: 8,1: 1.5～1: 8 and 1: the 1.5(weight ratio)
U: T=15～35%(weight)
Wherein S is β " (β)-aluminum oxide,
T is an epoxy glue
U is T
31, or T
651
B) CK-II coating:
The suitable environment temperature is 0 ℃～80 ℃,
S is phosphorus zirconium silicate or zirconium white
T is an epoxy glue,
When S be 100～160 orders or＞during 200 orders,
U is T
33, when the S granularity was＜40 orders, U was T
3, when the S granularity is＜40 orders, 100～160 orders, during＞200 orders,
T: S is respectively 1: 7,1: 1.5～1 6.5, and 1*
C) CK-III coating;
When-10 °～50 ℃ moist gaseous environments and low temperature (5 ℃), S selects β for use
11(β)-aluminum oxide,
T goes back organic silicic acid or polyurethane adhesive except that epoxy glue, U is T
33,
The same CK-1 of the size range of S, T: S and U: T,
D) CK-IV coating:
When acid gaseous environment and 150 °～300 ℃ hot environments enforcement galvanic protections,
S is β (β) aluminum oxide,
T is a water glass glue,
U is T*
When the granularity of S is＜40 orders, 100～160 orders, during＞200 orders, T: S is respectively 1: 6,1: 0.8～1: 6,1: 0.8, U: T was 3～10%(weight).
4, cathodic protector according to claim 1 is characterized in that described electronic conduction supplementary anode layer is:
A) form anode layer coating by Graphite Powder 99 (R) and binding agent (717)
B) spectrum graphite, alloy zinc, or with the metal of protected body material of the same race.
5,, it is characterized in that the proportioning of anode layer coating is according to the cathodic protector of claim 1 or 4:
When the R granularity is＜60 orders, during 100～200,200 orders, its R: * is respectively 1: 0.9,1: 0.2～0.8,1: 0.2(weight).
6, cathodic protector according to claim 1 is characterized in that in the protection potential measuring system impedance transformer being arranged, and it is made up of the unicircuit voltage follower of * negative supply power supply.
7, cathodic protector according to claim 1 is characterized in that described DC power supply equipment potentiostat, and its constant potential error is not more than 10 millivolts.
8, cathodic protector according to claim 1 is characterized in that the protection parameter computerized print recording unit in the described power supply system of DC source, can write down year simultaneously, month, day, the time, divide, second, received current, voltage, energising point current potential (φ
0) and 13 monitoring * current potential (φ
1～φ
13).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN86100581.3A CN1003525B (en) | 1986-05-21 | 1986-05-21 | Overhead metallic pipe cathode protector |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN86100581.3A CN1003525B (en) | 1986-05-21 | 1986-05-21 | Overhead metallic pipe cathode protector |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN86100581A CN86100581A (en) | 1987-12-02 |
| CN1003525B true CN1003525B (en) | 1989-03-08 |
Family
ID=4801108
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN86100581.3A Expired CN1003525B (en) | 1986-05-21 | 1986-05-21 | Overhead metallic pipe cathode protector |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1003525B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1035881C (en) * | 1993-05-21 | 1997-09-17 | 北京化工学院 | Anti-corrosive paint |
| CN101260526B (en) * | 2008-03-10 | 2013-07-24 | 中国人民解放军海军装备技术研究所 | Composite electric potential coupling corrosion control technique |
| CN102277578A (en) * | 2010-06-12 | 2011-12-14 | 中国海洋石油总公司 | ICCP (impressed current cathodic protection) method of leg type platform |
| CN102560502A (en) * | 2012-01-18 | 2012-07-11 | 中山市汇诚材料科技有限公司 | Auxiliary anode-flexible anode node sealing structure for cathodic protection |
| DE102012224269A1 (en) * | 2012-12-21 | 2014-06-26 | Robert Bosch Gmbh | Component of a fuel injection system |
| CN107236960B (en) * | 2017-06-22 | 2019-11-01 | 中国石油化工股份有限公司 | A kind of impressed current cathode protection device for oil expeller |
| CN107988603B (en) * | 2017-12-22 | 2023-07-07 | 郑州大学 | Device and method for protecting cable from corrosion by using externally applied current of rainwater conduction |
| CN112760655A (en) * | 2021-01-12 | 2021-05-07 | 广东海洋大学 | Combined protection technology for metal by utilizing coating and impressed current cathode in atmospheric environment |
| CN113186535B (en) * | 2021-04-22 | 2023-03-31 | 海信(广东)厨卫系统股份有限公司 | Solid electrolyte, preparation method thereof and cathode protection system |
-
1986
- 1986-05-21 CN CN86100581.3A patent/CN1003525B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN86100581A (en) | 1987-12-02 |
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