CN103149146A - Multifunctional corrosion monitoring probe used for monitoring corrosion of industrial equipment - Google Patents
Multifunctional corrosion monitoring probe used for monitoring corrosion of industrial equipment Download PDFInfo
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- CN103149146A CN103149146A CN2013100444012A CN201310044401A CN103149146A CN 103149146 A CN103149146 A CN 103149146A CN 2013100444012 A CN2013100444012 A CN 2013100444012A CN 201310044401 A CN201310044401 A CN 201310044401A CN 103149146 A CN103149146 A CN 103149146A
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Abstract
The invention discloses a multifunctional corrosion monitoring probe used for monitoring corrosion of industrial equipment and relates to corrosion electrochemistry monitoring equipment. The multifunctional corrosion monitoring probe is provided with central electrodes and n encirclement electrodes. The n encirclement electrodes are arranged around the central electrodes, the central electrodes and the n encirclement electrodes are packaged through insulation materials, and connection wires are arranged at the lower ends of the central electrodes and the lower ends of the n encirclement electrodes. Outer shells are arranged on outer sides of the insulation materials, and n is larger than or equal to two. By utilization of various electrochemical measuring technologies such as polarization resistance, alternating-current impedance and cyclic voltammetry, the corrosion status of the industrial equipment is monitored on line in real time. The multifunctional corrosion monitoring probe can be used for monitoring on line corrosion electrochemistry parameters, such as corrosion speed, corrosion potential, the polarization resistance, the alternating-current impedance and metal dissolved concentration, of the industrial equipment in service under the environment of water solution. The corrosion status of the industrial equipment in the production is comprehensively evaluated in real time. The multifunctional corrosion monitoring probe is especially suitable for monitoring and tracking service safety of large-scale industrial equipment such as a condensing tower, a heat exchanger, a rectifying tower, various reactors and a liquid delivery pipeline for a long time.
Description
Technical field
The present invention relates to the corrosion electrochemistry monitoring equipment, especially relate to a kind of Multifunctional corrosion monitoring probe for the corrosion of monitoring commercial unit.
Background technology
The commercial production operating mode is complicated, and environment is changeable, the easy corrosion of commercial unit.And the corrosion of commercial unit tends to reduce production efficiency, causes heavy economic losses, even causes serious burst accident.If adopt effectively online real-time corrosion monitoring technology, some key positions to commercial unit carry out the all-the-way tracking monitoring, in time understand its etch state, to scientific maintenance, the optimized production process of commercial unit, the great practical significance of enhancing productivity and keep the safety in production.
Traditional monitoring commercial unit corrosion both at home and abroad has the methods such as weight loss, spot thickness measurement, sonic flaw detection, chemical analysis, but these methods all are difficult to monitor in real time online the etch state of commercial unit.At present, adopt resistance probe, polarization curve exchange of technology impedance that the corrosion of commercial unit is monitored online in real time both at home and abroad.Pipeline soil sensor such as the people such as Yang Jinglin (Chinese patent CN201697859U) invention; The people such as Cao Jieyu (Chinese patent CN1590981) use the material identical with heat-exchange tube to make the etch state of probe monitoring heat-exchange tube; The on-line corrosion monitoring probe that the people such as Miao Jian (Chinese patent CN201060160) make can be applied in hanging slice method and electric-resistivity method together; People such as Guo Xingpeng (Chinese patent CN102128784A) etc. have invented the information that couple electrochemical noise corrosion monitoring probe can obtain the metal local corrosion delicately; But all can't monitor simultaneously the more fully information of the corrosion electrochemistry parameter such as corrosion potential, corrosion current, polarization resistance, AC impedance of commercial unit.
Summary of the invention
The object of the present invention is to provide a kind of Multifunctional corrosion monitoring probe for the corrosion of monitoring commercial unit.
The present invention is provided with central electrode and n props up around electrode, described n props up around electrode and is located at around central electrode, described central electrode and n prop up around electrode and are sealed by insulating material, described central electrode is connected with n around the lower end of electrode and establishes respectively the connection wire, the insulating material outside is provided with shell, and n is 〉=2 integer.
The material of described central electrode can adopt the metal or alloy such as carbon steel, stainless steel, copper, aluminium, and the diameter of described central electrode can be 1～20mm, and length is 3～30mm; Described central electrode can adopt the carbon steel cylindrical electrode, and the diameter of carbon steel cylindrical electrode can be 3～8mm, and length can be 5～15mm.
Described surrounding electric poles can adopt various inertia precious metal materials or graphite to make; Described various inertia noble metal can be selected from platinum, iridium, palladium, gold, titanium etc. or its alloy, and the diameter of surrounding electric poles can be 0.2～5mm, and length can be 3～30mm; Described surrounding electric poles is platinum electrode preferably, and the diameter of platinum electrode can be 0.5～2mm, and length can be 3～12mm.
N can be even number, and described surrounding electric poles preferably is symmetrically set in around central electrode.
Described central electrode be connected wire and can connect by being weldingly connected; Described surrounding electric poles be connected wire and can connect by being weldingly connected, seal its welding position with insulating material.
Described insulating material can be selected from a kind of in epoxy resin, silicon rubber, silicon dioxide, pottery, plastics, poly-tetrem alkene etc.
Described shell can adopt stainless steel casing, plastic casing or teflon shell etc.
The present invention is integrated central electrode and surrounding electric poles on every side; Can use the etch state of the multiple electrochemical measuring technology on-line real time monitoring commercial units such as polarization resistance, AC impedance, cyclic voltammetric.The present invention can be used for the corrosion electrochemistry parameters such as corrosion speed, corrosion potential, polarization resistance, AC impedance and dissolving metal concentration of commercial unit under the in commission aqueous environment of online Real-Time Monitoring, the etch state of the commercial unit during assessment is produced all sidedly in real time.Be specially adapted to the large industry equipments such as condensing tower, heat interchanger, rectification column, various reactor, liquid-transport pipe-line are on active service and carry out safely the long-term follow monitoring.
Description of drawings
Fig. 1 is that the structure of the embodiment of the present invention forms schematic diagram.
Fig. 2 is the FeSO of variable concentrations
4The cyclic voltammetry curve of solution.In Fig. 2, a is 0.0005M, and b is 0.001M, and c is 0.0025M, and d is 0.005M, and e is 0.0075M, and f is 0.01M, and g is 0.05M.
Fig. 3 is the partial enlarged drawing of Fig. 2.In Fig. 3, a is 0.0005M, and b is 0.001M, and c is 0.0025M, and d is 0.005M, and e is 0.0075M, and f is 0.01M, and g is 0.05M.
Fig. 4 is various concentration FeSO
4The oxidation peak current of solution circulation volt-ampere curve and Fe
2+The relation of concentration.
Fig. 5 is various concentration FeSO
4The reduction peak current of solution circulation volt-ampere curve and Fe
2+The relation of concentration.
Fig. 6 for central electrode take 20# as material at variable concentrations Na
2AC impedance spectrogram in S solution.In Fig. 5, a is 0.01molL
-1, b is 0.001molL
-1, c is 0.0001molL
-1, d is 0.00001molL
-1
Fig. 7 for central electrode take 20# as material at variable concentrations Na
2Polarization curve in S solution.In Fig. 6, mark ■ is 0.00001molL
-1, ● be 0.0001molL
-1, ▲ be 0.001molL
-1,
Be 0.01molL
-1
Embodiment
The invention will be further described below in conjunction with accompanying drawing and Application Example.
Referring to Fig. 1, the embodiment of the present invention is provided with central electrode 1 and 4 around electrode 2, described 4 are symmetrically set in around central electrode 1 around electrode 2, described central electrode 1 and 4 are sealed by insulating material 3 around electrode 2, described central electrode 1 connects wire 4 with being connected to establish respectively around the lower end of electrode 2, and insulating material 3 outsides are provided with shell 5.
Described central electrode 1 adopts the carbon steel cylindrical electrode, and the diameter of carbon steel cylindrical electrode can be 3～8mm, and length can be 5～15mm.
Described surrounding electric poles 2 adopts platinum electrode, and the diameter of platinum electrode can be 0.5～2mm, and length can be 3～12mm.
Described central electrode 1 be connected wire 4 and connect by being weldingly connected; Described surrounding electric poles 2 connects by being weldingly connected with being connected wire 4, seals its welding position with insulating material 3.
Described insulating material 3 adopts epoxy resin.
Described shell 5 adopts stainless steel casing.
Embodiment of the present invention manufacturing process is as follows:
The preparation of central electrode: choose the material identical with commercial unit to be monitored, as various Metal and Alloys such as carbon steel, stainless steel, copper, being processed into certain diameter is 1～20mm, length is the right cylinder of 3～30mm, a cylindrical end section is connected wire, other end cross section is cleaned through abrasive paper for metallograph polishing, absolute ethyl alcohol and pure water as workplace.
The preparation of surrounding electric poles on every side: the cut-off footpath is 0.2～5mm, and length is 3～30mm platinum filament or iridium wire, platinumiridio, graphite, titanium silk, and an end connects wire, then cleans with absolute ethyl alcohol and pure water.
With above-mentioned central electrode and on every side surrounding electric poles seal by certain distribution and dimensional requirement and be fixed in columned insulating material epoxy resin (surrounding electric poles can have 2,4,6,8,10 or more on every side, be symmetrically distributed in central electrode around).An end with abrasive paper for metallograph polishing epoxy resin exposes the smooth cross section of each electrode, then uses absolute ethyl alcohol and pure water ultrasonic cleaning.The other end of epoxy resin exposes the wire that is connected with electrode.
Selectively operating electrode and auxiliary electrode, if with central electrode as working electrode, surrounding electric poles as auxiliary electrode, can be measured with the technology of linear polarization and AC impedance the corrosion electrochemistry parameters such as corrosion of metal speed to be monitored, corrosion potential, polarization resistance, AC impedance on every side; Around also can part surrounding electric poles be as working electrode, with all the other surrounding electric poles as auxiliary electrode, with the concentration of metal ions in the commercial measurement solution of cyclic voltammetric.
Below provide the concrete manufacturing process for the Multifunctional corrosion monitoring probe of monitoring commercial unit corrosion:
Intercepting 20# carbon steel processing growth 10mm, the right cylinder of diameter 5mm is as central electrode; Intercept 4 long 4mm, the platinum filament of diameter 1mm be around surrounding electric poles.One end of every electrode all welds the copper conductor that is about 10cm.4 platinum electrodes are evenly distributed on around carbon steel electrode, and with epoxy resin enclosed one-tenth right cylinder, an end of epoxy resin exposes the cross section of above-mentioned each electrode, and the other end exposes the copper conductor that connects each electrode, as shown in Figure 1.Abrasive paper for metallograph polishes flat each electrode sections, then uses absolute ethyl alcohol and pure water ultrasonic cleaning.
The mensuration of Fe2+ concentration: compound concentration is respectively 5 * 10
-4M, 1 * 10
-3M, 2.5 * 10
-3M, 5 * 10
-3M, 7.5 * 10
-3M, 1 * 10
-2M, 5 * 10
-2The FeSO of M
4Solution adds a small amount of H in solution
2SO
4Prevent Fe
2+Hydrolysis oxidation, (H in solution in the present embodiment
2SO
4Concentration be all 0.001M), the solution of preparation passes into N
2Deoxygenation.Surveying instrument is the AUTOLAB electrochemical workstation, and as working electrode, all the other two conducts are to electrode with surrounding electric poles around two of Multifunctional corrosion monitoring probe, and saturated calomel electrode is as contrast electrode, the cyclic voltammetry curve of scanning different solutions.The condition of scan cycle volt-ampere curve is as follows: sweep limit is roughly relative open circuit potential ± 0.4V, sweep velocity 100mV/s.The FeSO of variable concentrations
4The cyclic voltammetry curve of solution is referring to Fig. 2 and 3.
Fig. 4 has shown the FeSO of several variable concentrations
4The CV curve of solution.Fig. 5 has shown oxidation peak current and the FeSO of CV curve
4The quantitative relation of solution concentration.Fig. 6 has shown reduction peak current and the FeSO of CV curve
4The quantitative relation of solution concentration.Draw oxidation peak current and reduction peak current and FeSO from figure
4Concentration has good linear relationship.Fe
2+The working curve of the relation of concentration and peak current can be with following two the Representation Equation: i
pa=1890C+3.9802;
i
pc=1500C+3.5155；
i
pa: oxidation peak current, μ A
i
pc: reduction peak current, μ A
C:Fe
2+Concentration, mol/L
Can determine that according to this equation GOLD FROM PLATING SOLUTION belongs to meltage or metal erosion speed.
The monitoring of metal erosion state:
Above-mentioned probe is polished with abrasive paper for metallograph, exposes bright and clean electrode surface, then use absolute ethyl alcohol and pure water ultrasonic.The Na of preparation variable concentrations
2S solution, take 20# carbon steel central electrode as working electrode, take around four platinum electrodes for to electrode, saturated calomel is contrast electrode, surveying instrument is the AUTOLAB electrochemical workstation, the technical research 20# carbon steel of employing linear polarization and AC impedance is at Na
2Corrosion behavior in S solution.Fig. 6 is the polarization curve of 20# carbon steel electrode, and Fig. 7 is the AC impedance spectrogram of 20# carbon steel electrode.
Corrosion potential, corrosion current, polarization resistance and the impedance of electrode in variable concentrations Na2S solution sees Table 1.
Table 1
| Na 2S concentration/molL -1 | 0.00001 | 0.0001 | 0.001 | 0.01 |
| Corrosion potential/mV | -0.725 | -0.746 | -0.763 | -0.780 |
| Corrosion electric current density/μ Acm -2 | 3.115 | 1.059 | 1.950 | 1.006 |
| Polarization resistance/K Ω | 5.75 | 6.95 | 4.74 | 6.43 |
| Charge transfer resistance/K Ω | 4.00 | 3.40 | 2.37 | 3.96 |
The corrosion electrochemistry parameters such as the corrosion potential of 20# carbon steel electrode, corrosion current, polarization resistance, impedance are subjected to S as seen from Table 1
2-Concentration as influencing factor.
The Multifunctional corrosion monitoring probe that hence one can see that makes can be used for monitoring the concentration of ordinary dissolution of corrosion potential, corrosion current, polarization resistance, impedance and the metal of commercial unit, this probe is used for the on-line corrosion monitoring system can comprehensively, in real time, precisely estimates commercial unit corrosion concentration and security.
Claims (10)
1. one kind is used for the Multifunctional corrosion monitoring probe that the monitoring commercial unit corrodes, it is characterized in that being provided with central electrode and n props up around electrode, described n props up around electrode and is located at around central electrode, described central electrode and n prop up around electrode and are sealed by insulating material, described central electrode is connected with n around the lower end of electrode and establishes respectively the connection wire, the insulating material outside is provided with shell, and n is 〉=2 integer.
2. a kind of Multifunctional corrosion monitoring probe for monitoring commercial unit corrosion as claimed in claim 1, is characterized in that the material of described central electrode adopts carbon steel, stainless steel, copper, aluminium or alloy.
3. a kind of Multifunctional corrosion monitoring probe for monitoring commercial unit corrosion as claimed in claim 1, the diameter that it is characterized in that described central electrode is 1～20mm, length 3～30mm.
4. a kind of Multifunctional corrosion monitoring probe for monitoring commercial unit corrosion as claimed in claim 1, is characterized in that described central electrode adopts the carbon steel cylindrical electrode, and the diameter of carbon steel cylindrical electrode is 3～8mm, and length is 5～15mm.
5. a kind of Multifunctional corrosion monitoring probe for monitoring commercial unit corrosion as claimed in claim 1, is characterized in that described surrounding electric poles adopts inertia precious metal material or graphite to make; Described inertia noble metal is selected from platinum, iridium, palladium, gold, titanium or its alloy, and the diameter of surrounding electric poles can be 0.2～5mm, and length can be 3～30mm.
6. a kind of Multifunctional corrosion monitoring probe for monitoring commercial unit corrosion as claimed in claim 1, is characterized in that described surrounding electric poles is platinum electrode, and the diameter of platinum electrode is 0.5～2mm, and length is 3～12mm.
7. a kind of Multifunctional corrosion monitoring probe for monitoring commercial unit corrosion as claimed in claim 1, is characterized in that n is even number, and described surrounding electric poles is symmetrically set in around central electrode.
8. a kind of Multifunctional corrosion monitoring probe for monitoring commercial unit corrosion as claimed in claim 1 is characterized in that described central electrode and is connected wire and connects by being weldingly connected; Described surrounding electric poles connects by being weldingly connected with being connected wire, seals its welding position with insulating material.
9. a kind of Multifunctional corrosion monitoring probe for monitoring commercial unit corrosion as claimed in claim 1 is characterized in that described insulating material is selected from a kind of in epoxy resin, silicon rubber, silicon dioxide, pottery, plastics, poly-tetrem alkene.
10. a kind of Multifunctional corrosion monitoring probe for monitoring commercial unit corrosion as claimed in claim 1, is characterized in that described shell adopts stainless steel casing, plastic casing or teflon shell.
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Cited By (13)
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| CN103439532A (en) * | 2013-09-02 | 2013-12-11 | 厦门乐钢材料科技有限公司 | Microelectrode technology for metal surface microcell current distribution in-situ detection |
| CN103558077A (en) * | 2013-11-06 | 2014-02-05 | 上海电机学院 | Packaging method for electrochemical testing sample |
| CN103954664A (en) * | 2014-04-10 | 2014-07-30 | 深圳普门科技有限公司 | Electrode disk, preparation method thereof and electrochemical flow cell based on same |
| CN105021519A (en) * | 2015-08-13 | 2015-11-04 | 中国石油化工股份有限公司 | On-line atmospheric corrosion measuring device |
| ES2573178A1 (en) * | 2015-09-18 | 2016-06-06 | Universidad Complutense De Madrid | Sensor for the monitoring of corrosión by electrochemical and impedance measurements and resistance to polarization and use thereof (Machine-translation by Google Translate, not legally binding) |
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| CN105021519A (en) * | 2015-08-13 | 2015-11-04 | 中国石油化工股份有限公司 | On-line atmospheric corrosion measuring device |
| WO2017046427A1 (en) * | 2015-09-18 | 2017-03-23 | Universidad Complutense De Madrid | Sensor for monitoring corrosion by means of measurements of electrochemical impedance and noise and of resistance to polarisation and use of same |
| ES2573178A1 (en) * | 2015-09-18 | 2016-06-06 | Universidad Complutense De Madrid | Sensor for the monitoring of corrosión by electrochemical and impedance measurements and resistance to polarization and use thereof (Machine-translation by Google Translate, not legally binding) |
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| CN107144613A (en) * | 2017-05-09 | 2017-09-08 | 中国石油大学(华东) | Three electrod-array Local electrochemical information test systems and method of testing |
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| CN107655814A (en) * | 2017-11-15 | 2018-02-02 | 上海大学 | The high-flux detection method that alloying element influences for mild steel decay resistance |
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| CN110243911B (en) * | 2019-07-04 | 2021-06-08 | 华南理工大学 | Ion selective electrode for fast detecting concrete pore solution chloride ion and its manufacture |
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| CN112461745A (en) * | 2020-11-05 | 2021-03-09 | 中国科学院海洋研究所 | Electrochemical probe and measuring method for on-site monitoring corrosion of weathering steel rust layer |
| CN112461745B (en) * | 2020-11-05 | 2022-09-27 | 中国科学院海洋研究所 | Electrochemical probe and measuring method for on-site monitoring corrosion of weathering steel rust layer |
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Application publication date: 20130612 |