CN103822872B - Dew point corrosion monitoring method based on electrochemical noise - Google Patents
Dew point corrosion monitoring method based on electrochemical noise Download PDFInfo
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- CN103822872B CN103822872B CN201310493129.6A CN201310493129A CN103822872B CN 103822872 B CN103822872 B CN 103822872B CN 201310493129 A CN201310493129 A CN 201310493129A CN 103822872 B CN103822872 B CN 103822872B
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Abstract
The invention relates to a dew point corrosion monitoring method based on electrochemical noise, and mainly solves the problem that a dew point corrosion condition cannot be reflected in a real-time manner in the prior art. The method adopts the technical scheme that main components comprising a three-electrode-assembly probe, a zero-resistance ammeter, a high-resistance voltmeter, an A/D convertor and a computer are adopted; the three-electrode-assembly probe comprises a reference electrode assembly and two working electrode assemblies, and the reference electrode assembly is connected with the high-resistance voltmeter; the first working electrode assembly is connected with the zero-resistance ammeter and the high-resistance voltmeter respectively, and the second working electrode assembly is connected with the zero-resistance ammeter; potential noise generated by the high-resistance voltmeter and current noises generated by the zero-resistance ammeter enter the A/D convertor, and the A/D convertor is connected with the computer; the reference electrode assembly comprises at least one reference electrode, the first working electrode assembly comprises at least one working electrode, and the second working electrode assembly comprises at least one working electrode. The technical scheme well solves the problem. The dew point corrosion monitoring method can be used in dew point corrosion monitoring of oil refineries.
Description
Technical field
The present invention relates to a kind of dew point corrosion monitoring method based on electrochemistry noise.
Technical background
In oil plant, heating furnace air preheater and flue, Economizer of Heat Recovery Boiler and pipeline, cylindric heater furnace wall with
And all there is dew point corrosion problem in various overhead condensation cooling system, tank deck gas-liquid phase transition position etc..Existing dew point corrosion monitoring
Method is mainly measurement dew point temperature or weight loss, and the result being given is an indirect parameter or average corruption interior for a long time
Erosion speed.Practical situation be when flue gas, aqueous vapor, oil gas temperature more than dew point temperature when, substantially will not cause corruption to equipment
Erosion；And work as temperature and drop to below critical temperature, corrode when condensing and form liquid film in metal surface, on corrosion rate is rapid
Rise, existing monitoring method can not reflect dew point corrosion situation in real time.
Electrochemical noise technique has the advantages that to tested systems undisturbed, can achieve continuous monitoring, and can reflect local
Corrosion information.United States Patent (USP) us patent5,139,627 proposes one kind electrochemistry noise (en) technology for detection metal surface
The method and apparatus of corrosion.This equipment adopts same material three-electrode system, and measuring electrode material occurs corrosion anti-in the environment
Answer produced current potential noise (epn) and current noise (ecn) signal, description corrosion speed can be obtained by certain computational methods
Rate and the parameter of corrosion type.United States Patent (USP) us patent6,264,824b1 devise similar measuring system, at data
The method adopting statistical analysiss in reason, is come anti-by noise resistance, spot corrosion index, the skewness and kurtosis of signal, probability distribution etc.
Reflect homogeneous corrosion and local corrosion condition.It is rotten that Chinese patent cn101017128a provides a kind of local based on electrochemistry noise
Erosion analysis method and device, this device adopts four electrode catheters, and carries out segmentation statistics and cluster analyses to noise data, is given
Etch state.But their designed electrode systems are all only suitable for continuous electrolysis matter, and this liquid film does not connect for dew point corrosion
Continuous, unstable situation is inapplicable.
Atmospheric corrosion belongs to the electrochemical corrosion under thin liquid film as dew point corrosion, Corrosion Monitor (acm)
The dissimilar metal bipolar electrode that sensor is generally closely and alternatively arranged, will produce galvanic couple when there being thin liquid film to cover between electrode
Electric current, can reflect wetting time and corrosiveness of the environment by measuring Galvanic Current.But acm can not provide the uniform of electrode material
With local corrosion condition.
The present invention is based on electrochemistry noise method, solves the monitoring problem of oil plant dew point corrosion, especially supervises online
Survey problem.
Content of the invention
The technical problem to be solved is can not be using the refining of electrochemistry noise method on-line monitoring in prior art
The problem of oily factory dew point corrosion, provides a kind of new dew point corrosion monitoring method based on electrochemistry noise.The method is used for refining
In the dew point corrosion monitoring of oily factory, have the advantages that simple, lossless, be capable of real time on-line monitoring, enrich refining equipment
The monitoring meanss of dew point corrosion.
For solving the above problems, the technical solution used in the present invention is as follows: critical piece includes three electrode group probes, zero resistance
Galvanometer, high resistance voltmeter, a/d transducer and computer, described three electrode group probes include a reference electrode group and two
Working electrode group, reference electrode group is connected with high resistance voltmeter, and the first working electrode group hinders galvanometer, high resistant voltage with zero respectively
Table is connected, and the second working electrode group is connected with zero resistance galvanometer, and the current potential noise that high resistance voltmeter produces, zero resistance galvanometer produce
Current noise enter a/d transducer, a/d transducer is connected with computer, and described reference electrode group includes at least one reference
Electrode, described first working electrode group includes at least one working electrode, and described second working electrode group includes at least one work
Make electrode, described first working electrode is with the second working electrode, working electrode and reference electrode and is staggered, and does not mutually connect
Touch.
In technique scheme, described three electrode group probes are made up of compact arranged same material electrode, and material selects
The same or like material in position surveyed with equipment；Described three electrode groups probes are placed in equipment under test dew point corrosion easily occurs
Suitable position, when gas is in three electrode group detecting head surface condensation and dewfalls, zero resistance galvanometer shows electric current and produces.High resistant voltage
The current potential noise signal of table and zero resistance galvanometer collection inputs computer through a/d transducer, judges current signal by related software
Whether it is zero, the explanation no dew point corrosion when electric current is zero occurs, and automatically records current potential and current signal when electric current is not zero,
And corrosion parameter is calculated according to formula；Described dew point corrosion monitoring can real-time online be carried out；Described high resistance voltmeter at least 1,000,000
The voltage of ohm；Described reference electrode group includes a reference electrode, and described first working electrode group includes a working electrode,
Described second working electrode group includes a working electrode；Folder lining heat insulating lamella between described adjacent electrode.
During using assembly of the invention, probe is placed in the suitable position that equipment under test easily occurs dew point corrosion, works as flue gas
In detecting head surface condensation and dewfall, covered by liquid film between electrode group and turn on, zero resistance galvanometer shows electric current and produces.High resistant
The current noise signal of the current potential noise signal of voltmeter collection and zero resistance galvanometer collection inputs computer through a/d transducer,
Judge whether current signal is zero by software, when electric current is zero explanation no dew point corrosion occur, record no dew point corrosion when
Section, automatically records current potential and current signal when electric current is not zero, and calculates noise resistance, spot corrosion index, current potential and electric current
The corrosion parameters such as the skewness and kurtosis of signal, can reflect uniform and local corrosion condition.There is provided a kind of based on electrochemistry noise
Dew point corrosion monitoring method.It can improve and integrate prior art, devise compact arranged same material three electrode group, will
Electrochemical noise technique is applied to the monitoring of refining equipment dew point corrosion, synchro measure current potential and current noise signal, calculates and sends out
Uniform and local corrosion parameter during raw dew point corrosion.Assembly of the invention can measure actual condition and divide into preparation raw dew point corruption
The period of erosion and corrosion condition, have the advantages that simple, lossless, are capable of real time on-line monitoring, enrich refining equipment dew
The monitoring meanss of spot corrosion, achieve preferable technique effect.
Below by embodiment, the invention will be further elaborated, but is not limited only to the present embodiment.
Specific embodiment
[embodiment 1]
Dew point corrosion electrochemistry noise monitoring device of the present invention is popped one's head in by three electrode groups, high resistance voltmeter, zero resistance electricity
Flowmeter, a/d transducer and computer and corresponding software composition can on-line monitorings.Three electrode groups are popped one's head in by compact arranged material of the same race
Material electrode composition, material selects the same or like material in position surveyed with equipment, so that truly reflection equipment corrosion situation.Will
Material makes long 20 millimeters, wide 2 millimeters of little cube electrode, folder lining heat insulating lamella between adjacent electrode, about 0.2 millimeter of spacing, according to
The order arrangement (wherein w1 is the first working electrode, w2 is the second working electrode, r is reference electrode) of w1w2rw1w2rw1w2,
Use resistant to elevated temperatures epoxy encapsulation.These electrodes are aggregated into three groups with wire connection, respectively as reference electrode, the first work
Electrode and the second working electrode.
During using assembly of the invention, probe is placed in the suitable position that equipment under test easily occurs dew point corrosion, works as flue gas
In detecting head surface condensation and dewfall, covered by liquid film between electrode group r, w1 and w2 and turn on, zero resistance galvanometer shows electric current
Produce.Electricity between w1 and w2 of the current potential noise signal between r and w1 of high resistance voltmeter collection and zero resistance galvanometer collection
Flow noise signal inputs computer through a/d transducer 4, judges whether current signal is zero by software, the explanation when electric current is zero
No dew point corrosion occurs, and the period of record no dew point corrosion, automatically records current potential and current signal when electric current is not zero, and root
Calculate noise resistance rn, degree of bias sk of spot corrosion index li, current potential and current signal and kurtosis ku according to formula, wherein utilize rn simultaneously
Cooperation other specification can reflect uniform corrosion rate, and the Changing Pattern of li, sk and ku can be used to reflect that local corrosion is inclined to.Sampling
Frequency setting is 2hz, calculated one group of corrosion parameter every 1024 seconds (about 17 minutes),
Above-mentioned several electrochemistry noise parameter is all based on glucose current equation signal is carried out with the result of statistical analysiss.
Wherein noise resistance rn:
σ e and σ i is the standard deviation of current potential or current signal.Generally rn and uniform corrosion rate are in inverse ratio, and with polarization
Resistance rp is close.
Spot corrosion index li:
σ i is the standard deviation of current signal, rmsiRoot-mean-square for current signal.It is generally believed that li close to 1 when, show
The generation of local corrosion；And close to 0, li means that electrode surface homogeneous corrosion or keeps passive state.
Degree of bias sk:
Xi is actual measurement current potential or current value,For meansigma methodss, σ is the standard deviation of current potential or electric current, and n is sampling number.Partially
Degree describes the symmetry of noise data distributional pattern, and during the degree of bias=0, distributional pattern is symmetrical with regard to average.The noise of homogeneous corrosion
The signal degree of bias is close to 0.
Kurtosis ku:
Xi is actual measurement current potential or current value,For meansigma methodss, σ is the standard deviation of current potential or electric current, and n is sampling number.Peak
Degree describes the suddenly slow degree of noise data distributional pattern, and during kurtosis=3, distributional pattern is identical with the suddenly slow degree of normal distribution.
The noise signal kurtosis of homogeneous corrosion is close to 3.
Obviously, using the method for the present invention, can reach rotten using electrochemistry noise method on-line monitoring oil plant dew point
The purpose of erosion, has larger technical advantage, can be used in the monitoring of oil plant dew point corrosion.
Claims (3)
1. a kind of dew point corrosion monitoring method based on electrochemistry noise, critical piece includes three electrode group probes, zero resistance electric current
Meter, high resistance voltmeter, a/d transducer and computer, described three electrode group probes include a reference electrode group and two work
Electrode group, reference electrode group is connected with high resistance voltmeter, and the first working electrode group hinders galvanometer, high resistance voltmeter phase with zero respectively
Even, the second working electrode group is connected with zero resistance galvanometer, the electricity that the current potential noise of high resistance voltmeter generation, zero resistance galvanometer produce
Flow noise enters a/d transducer, and a/d transducer is connected with computer, and described reference electrode group includes at least one reference electrode,
Described first working electrode group includes at least one working electrode, and described second working electrode group includes at least one work electricity
Pole, described first working electrode is with the second working electrode, working electrode and reference electrode and is staggered, and is not in contact with each other；Institute
State reference electrode group and include a reference electrode, described first working electrode group includes a working electrode, described second work
Electrode group includes a working electrode；Folder lining heat insulating lamella between described adjacent electrode；Described by three electrode groups probe be placed in tested
Easily there is the suitable position of dew point corrosion in equipment, when gas is in three electrode group detecting head surface condensation and dewfalls, zero resistance galvanometer shows
It is shown with electric current to produce, the current potential noise signal of high resistance voltmeter and zero resistance galvanometer collection inputs computer through a/d transducer, by
Related software judges whether current signal is zero, and the explanation no dew point corrosion when electric current is zero occurs, when electric current is not zero certainly
Dynamic record current potential and current signal, and corrosion parameter is calculated according to formula；The electricity that at least 1 megohm of described high resistance voltmeter
Pressure.
2. according to claim 1 the dew point corrosion monitoring method based on electrochemistry noise it is characterised in that described three electrodes
Group probe is made up of compact arranged same material electrode, and material selects the same or like material in position surveyed with equipment.
3. according to claim 1 the dew point corrosion monitoring method based on electrochemistry noise it is characterised in that described dew point is rotten
Erosion monitoring can real-time online be carried out.
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| CN104502267A (en) * | 2014-12-31 | 2015-04-08 | 天津大学 | Electrochemical noise corrosion type distinguishing method based on support vector machine |
| CN104502265A (en) * | 2014-12-31 | 2015-04-08 | 天津大学 | Electrochemical noise testing method under normal temperature and normal pressure |
| CN108061704A (en) * | 2017-12-06 | 2018-05-22 | 中国石油大学(华东) | A kind of single electrode crossed array wire beam electrode system corroded under Test coverage object |
| CN109033446B (en) * | 2018-08-20 | 2020-08-04 | 中石化（洛阳）科技有限公司 | Corrosion type judging method and device |
| CN112782256A (en) * | 2019-11-06 | 2021-05-11 | 中国石油化工股份有限公司 | Multi-parameter probe for corrosion monitoring and corrosion detection system |
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| GB8611518D0 (en) * | 1986-05-12 | 1986-06-18 | Manchester Inst Science Tech | Corrosion monitoring |
| JPH09159601A (en) * | 1995-12-08 | 1997-06-20 | Babcock Hitachi Kk | Method and apparatus for predicting corrosion of metallic material |
| US6264824B1 (en) * | 1998-02-20 | 2001-07-24 | Integriti Investments Ltd. | Assessment of corrosion |
| CN2750317Y (en) * | 2004-12-09 | 2006-01-04 | 中国船舶重工集团公司第七二五研究所 | Multi-channel galvanic corrosion experiment data collecting device |
| JP2006258602A (en) * | 2005-03-17 | 2006-09-28 | Ebara Corp | Probe for monitoring dew point corrosion |
| CN100485362C (en) * | 2006-10-13 | 2009-05-06 | 华中科技大学 | Analysis method and devicefor localized corroding based on electrochemistry noise |
| WO2010002831A2 (en) * | 2008-07-02 | 2010-01-07 | Pepperl + Fuchs, Inc. | Electrochemical noise as a localized corrosion indicator |
| CN102507430B (en) * | 2011-11-11 | 2014-04-16 | 天津亿利科能源科技发展股份有限公司 | Online monitoring device for corrosion in pipeline |
| CN102692438B (en) * | 2012-06-15 | 2014-03-26 | 哈尔滨工程大学 | Dew point corrosion experiment device capable of realizing electrochemical tests |
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