CN108535178A - A kind of corrosive pipeline rate on-Line Monitor Device and on-line monitoring method - Google Patents
A kind of corrosive pipeline rate on-Line Monitor Device and on-line monitoring method Download PDFInfo
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- G—PHYSICS
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- G01N17/00—Investigating resistance of materials to the weather, to corrosion, or to light
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Abstract
The invention discloses a kind of corrosive pipeline rate on-Line Monitor Device and on-line monitoring method, which includes：The method of electrochemical test system, lacing film system and corresponding valve, flowmeter etc., corrosion rate on-line monitoring includes the following steps：(1) it installs to be monitored to electrode and corrosion coupon, adjusts consistent with flow velocity in system pipeline by the flow rate of liquid of device；(2) linear polarization method is used to measure linear polarization resistance；(3) solution resistance between galvanostatic method measuring electrode is used；(4) it subtracts the value of solution resistance with linear polarization resistance divided by 2 obtains anode polarization resistance Rp”；(5) B values are obtained with weight loss correction method；(6) corrosion rate Icorr=B/Rp”；The present invention passes through to anode polarization resistance Rp" the obtained B values of Accurate Determining and weight loss correction method real-time, accurate, the continuous on-line monitoring to pipeline corrosion rate may be implemented.
Description
Technical field
The invention belongs to corrosion electrochemistry fields, are related to fluid corrosiveness measuring technology, and in particular to a kind of corrosive pipeline
Rate on-Line Monitor Device and on-line monitoring method.
Background technology
Solution inside metallic conduit can cause to corrode to it, corrosion failure generate leakage can result in waste of resources, ring
Border is polluted, and influences normal production and living, causes the loss of human life's property.Currently, the method for on-line corrosion monitoring
Mainly have, weight loss method, resistance probe method, linear polarization method, electrochemistry noise method, the advantages of each method has oneself and
Limitation.It is weight loss method economy, simple, but the method needs complicated experiment post analysis, can not monitor in real time, experiment week
Phase is long；Resistance probe method is sensitive, facilitates and can continuously monitor, but the method can only measure the accumulative corrosion in a period of time
Amount, cannot measure instantaneous corrosion rate and local corrosion；Linear polarization method can quickly measure the instantaneous corrosion rate of metal, but
It is that the method is not suitable in the medium of poorly conductive；Electrochemistry noise method measuring device is simple, is not required to external disturbance, to tested
System does not interfere with, but the electrical state random fluctuation of itself in Process of Metallic Corrosion, chemical signal and corrosion metal electricity
Complete test system is not set up between pole still so far.
Currently, existing corrosion monitoring process can not all realize monitoring in real time and stablize accurate measurement or monitoring simultaneously
Period length or fluctuation of service, it is more to be disturbed factor.
Invention content
For overcome the deficiencies in the prior art, the present invention provides a kind of corrosive pipeline rate on-Line Monitor Device and online
Monitoring method, this method are improved linear polarization method, and using two-electrode system, solution electricity is accurately measured using galvanostatic method
Resistance, excludes the influence of solution resistance, solves the qualifications that linear polarization method is not suitable for poorly conductive medium, use lacing film
The mode that weight-loss method is combined with polarisation resistance method accurately obtains the B values in Stern formula, follow-up only to need after accurately obtaining B values
Real-time corrosion rate is can be obtained by after measuring real-time anode polarization resistance value.
To achieve the above objectives, the present invention adopts the following technical scheme that：
A kind of corrosive pipeline rate on-Line Monitor Device is included in the front and back on-Line Monitor Device being arranged in Monitoring Pinpelines position
Inlet ball valve 1 and on-Line Monitor Device vent ball valve 10 are provided with flow on the pipeline in 1 downstream of on-Line Monitor Device inlet ball valve
2 are counted, pair for test of the clamping of bipolar electrode electro-chemical test electrode clamping device 3 is provided on the pipeline in 2 downstream of flowmeter
The pipeline of electrode 4,4 downstream of bipolar electrode for test divides two-way, is provided with hanger device inlet ball valve 7 on pipeline all the way and hangs
Sheet devices 8, are provided with hanger device bypass ball valve 6 on another way pipeline, two-way pipeline merge after pipeline on be provided with it is online
Monitoring device vent ball valve 10；Further include the Electrochemical Comprehensive Tester 5 being connected with the bipolar electrode 4 for test, setting is hung
Corrosion coupon 9 in sheet devices 8.
The bipolar electrode electro-chemical test electrode clamping device 3 is process for organic glass, and internal is the logical of rectangle
Road, is equipped with the opposite bipolar electrode 4 for test at the symmetrical side-wall hole of rectangular channel, and tapping tapping thread is double
Standard size of flange is processed at electrode electro Chemical test electrode clamping device both ends, is connected by bolt with the flange welded on pipeline
It connects.
The bipolar electrode 4 for test is that polytetrafluoro bar 11 is process with metal bar 12, in polytetrafluoro bar
The embedded metal bar 12 with monitoring pipeline same material among 11,11 one end external threading of polytetrafluoro bar, with bipolar electrode electricity
3 internal thread of test chemical electrode clamping device matches, and the other end is processed as hexagon, facilitates and is fastened and drawn with spanner
Metallic rod is convenient to be connect with Electrochemical Comprehensive Tester 5.
The hanger device 8 is process for organic glass, and inside is circular channel, channel cross-sectional area and bipolar electrode electrification
The inner passage sectional area for learning test electrode clamping device 3 is identical, and standard size of flange is processed at both ends, convenient to be welded on pipeline
The flange connect is bolted；
The corrosion coupon 9 is standard test piece identical with pipe material, and the punching of test piece both ends is connected and consolidated by fishing line
It is scheduled in hanger device 8.
The on-line monitoring method of the corrosive pipeline rate on-Line Monitor Device, includes the following steps：
Step 1, according to corrosive pipeline monitor position it needs to be determined that the position of corrosive pipeline on-Line Monitor Device, according to pipe
The medium flow direction short circuit that forward and backward opening is welded the primary door of import and export and extended near Monitoring Pinpelines position, corrosion exist in road
Line monitoring device is welded to connect by on-Line Monitor Device inlet ball valve 1 and on-Line Monitor Device vent ball valve 10 with short circuit；
Step 2, the liquid in pipeline passes sequentially through on-line corrosion monitoring device inlet ball valve 1, flowmeter 2, bipolar electrode electricity
Test chemical electrode clamping device 3 and electrode 4 for test, electrode 4 are connected with Electrochemical Comprehensive Tester 5, then, liquid
Body bypasses ball valve 6, most by hanger device inlet ball valve 7, hanger device 8 and corrosion coupon 9 or directly by hanger device
It is returned in monitoring pipeline by on-Line Monitor Device vent ball valve 10；
Step 3, open on-Line Monitor Device vent ball valve 10, close hanger device and bypass ball valve 6, open hanger device into
Mouth ball valve 7 is clamped to control by bipolar electrode electro-chemical test electrode by adjusting the aperture of on-Line Monitor Device inlet ball valve 1
The flow velocity of device 3 and hanger device 8 is consistent with the flow velocity of solution in institute monitoring pipeline, runs 3 days, passes through electrochemistry integration test
Instrument 5 is measured every 4h for the solution resistance R between the bipolar electrode 4 of testsol, a pair of bipolar electrode 4 for test is measured every 4h
Between linear polarization resistance Rp' take the average value R of linear polarization resistance in 3 daysP is flatAnd the average value R of solution resistanceSol is flat, with linear
The average value R of polarization resistanceP is flatSubtract the average value R of solution resistanceSol is flat, obtain excluding the electrode polarization electricity that solution resistance influences
Hinder Rp', with the electrode polarization resistance R for excluding solution resistance influencep' divided by 2 obtain anode polarization resistance Rp", take out hanger device
Corrosion coupon 9 in 8 cleans out 9 surface corrosion product of corrosion coupon, the corrosion of corrosion coupon 9 is calculated by weight-loss method
Rate ICorr is weightless, B=I is obtained according to Stern formulaCorr is weightless·Rp”；
Step 4, open on-Line Monitor Device vent ball valve 10, open hanger device and bypass ball valve 6, close hanger device into
Mouth ball valve 7, flow velocity and the institute by electrode clamping device 3 are controlled by adjusting the aperture of on-Line Monitor Device inlet ball valve 1
The flow velocity for monitoring solution in pipeline is consistent, measures the real-time polarization resistance R in 4 surface of bipolar electrode for testP is real-timeAnd in real time
Solution resistance Rsol is real-time, with real-time polarization resistance RP is real-timeSubtract real-time solution resistance RSol is real-time, obtain excluding solution resistance
The real-time electrode polarization resistance R influencedP is real-time', with the real-time electrode polarization resistance R for excluding solution resistance influenceP is real-time' divided by 2
Obtain real-time anode polarization resistance RP is real-time", monitored gold is directly obtained according to Stern formula by the B values obtained in step 3
The real-time corrosion rate I in metal conduit surfaceCorr is real-time=B/RP is real-time″。
Choose the maximum position of flow velocity in pipeline in corrosive pipeline monitoring position described in step 1；Described in step 1
The primary door of import and export and the short circuit extended are welded in time after draining the solution in pipeline during equipment out of use, convenient
The installation of subsequent corrosion on-line monitoring equipment.
For the solution resistance R between the bipolar electrode 4 of test in the step 3solMeasurement use galvanostatic charge curve methodology, in
0s~5s imposes step current I between the bipolar electrode 4 for testsolAnd record the value E of voltage between bipolar electrodesol, in the time
For 0s when resistance be solution resistance Rsol=Esol/Isol；
For the linear polarization resistance R between the bipolar electrode 4 of test in the step 3pMeasurement, using linear polarization method,
Scanning range is the sweep speed 20mV/min relative to open circuit potential ± 10mV, linear polarization resistance R between the bipolar electrodepFor
Electrode polarization resistance Rp' and solution resistance RsolSum, thus be excluded that solution resistance influence electrode polarization resistance Rp'=Rp-
Rsol；
The step 3 Anodic polarization resistance Rp" measurement, since two-electrode system does not have reference electrode, when outer power-up
When stream passes through anode and cathode, anode potential deviates equilibrium potential to shuffling, and cathode potential deviates equilibrium potential to negative shifting, and two
Person is carried out at the same time, and absolute value is equal；Polarization potential under the conditions of this is potential difference △ E of the anode relative to cathode, at this time △ E
=△ ESun-△EIt is cloudy, since cathodic polarization potential is negative value, so △ E=△ ESun+|△EIt is cloudy|=2 × △ ESun, △ ESun=△ E/2,
It is linear relationship in linear polarized area polarization potential and polarization resistance, therefore anode polarization resistance Rp"=Rp'/2。
Stern formula I in the step 3corr=B/Rp' B be Stern constant, be not under certain monitoring of environmental
The constant of change.
Compared to the prior art compared with, the invention has the advantages that：
1, three-electrode system is replaced using two-electrode system, it is small by such environmental effects, it can be applied to the ring with pressure
Border.
2, solution resistance is accurately measured using galvanostatic method, solution resistance is to measuring when exclusion electrical conductivity of solution is smaller
The influence brought solves the qualifications that linear polarization method is not suitable for poorly conductive medium.
3, the B values in Stern formula are accurately obtained using the mode that weight loss method is combined with polarisation resistance method, accurately
After obtaining B values, subsequently only needs to measure real-time anode polarization resistance value and solution resistance value can be obtained by real-time corrosion
Rate.
4, this method is easy to operate, and noiseless factor, time of measuring is short, and data are accurate.
Description of the drawings
Fig. 1 is monitoring device structural schematic diagram of the present invention.
Fig. 2 is the front view and vertical view of electrode of the present invention, and wherein Fig. 2 a are front view, and Fig. 2 b are vertical view.
Fig. 3 is electrode clamping device schematic diagram of the present invention.
Specific implementation mode：
As shown in Figure 1, the bypass of inventive pipeline corrosion rate on-Line Monitor Device is installed on Near Pipelines to be monitored, it can
Corrosion rate inside metallic conduit is monitored in real time comprising electrochemical test system, lacing film system and corresponding valve
Door, flowmeter etc..Medium in pipeline passes sequentially through on-Line Monitor Device inlet ball valve 1, flowmeter 2, bipolar electrode electrochemistry and surveys
Electrode clamping device 3 and the bipolar electrode 4 for test are tried, the bipolar electrode 4 for test is connected with Electrochemical Comprehensive Tester 5
Connect, then, medium by hanger device inlet ball valve 7, hanger device 8 and corrosion coupon 9 or directly by hanger device by
Road ball valve 6 is most returned to through on-Line Monitor Device vent ball valve 10 in monitoring pipeline afterwards.
The measurement for carrying out B values first, 4 surface of bipolar electrode polished successively for test with the sand paper of different model, such as Fig. 2
Shown, the bipolar electrode 4 for test is that polytetrafluoro bar 11 is process with metal bar 12, embedding among polytetrafluoro bar 11
Enter with the metal bar of pipeline same material 12, each 4 one first tap external screw thread of bipolar electrode for test, other end is processed as six
It is angular, facilitate and fastened with spanner, as shown in figure 3, by bipolar electrode electro-chemical test electricity is fixed on for the bipolar electrode 4 of test
On pole clamping device 3, bipolar electrode electro-chemical test electrode clamping device 3 is process for organic glass, and internal is rectangle
Channel, in the symmetrical side-wall hole of rectangular channel to install the bipolar electrode 4 for test, tapping tapping thread, with for
The bipolar electrode 4 of test matches.Corrosion coupon 9 is connected with fishing line, is fixed in hanger device 8.Open on-Line Monitor Device
Vent ball valve 10 closes hanger device and bypasses ball valve 6, open hanger device inlet ball valve 7, adjusts on-Line Monitor Device inlet ball
The aperture of valve 1 flows through in the flow velocity and monitoring pipeline of bipolar electrode electro-chemical test electrode clamping device 3 and hanger device 8
Flow velocity is consistent, runs 3 days, by Electrochemical Comprehensive Tester 5 between 4h measures the bipolar electrode 4 for test with galvanostatic method
Solution resistance Rsol, the linear polarization resistance R between a pair of bipolar electrode 4 for test is measured every 4h linear polarization methodsp’
Take the average value R of linear polarization resistance in 3 daysP is flatAnd the average value R of solution resistanceSol is flat, with the average value R of linear polarization resistanceP is flat
Subtract the average value R of solution resistanceSol is flatIt obtains excluding the electrode polarization resistance R that solution resistance influencesp', with exclusion solution resistance
The electrode polarization resistance R of influencep' divided by 2 obtain anode polarization resistance Rp", take out the corrosion coupon 9 in hanger device 8, cleaning
9 surface corrosion product of clean corrosion coupon, corrosion rate I is calculated by weight-loss methodCorr is weightless, B is obtained according to Stern formula
=ICorr is weightless·Rp”。
After knowing B values, on-Line Monitor Device vent ball valve 10 is opened, hanger device is opened and bypasses ball valve 6, closes lacing film dress
Inlet ball valve 7 is set, the flow velocity by electrode clamping device 3 is controlled by adjusting the aperture of on-Line Monitor Device inlet ball valve 1
It is consistent with the flow velocity in monitoring pipeline.Measure double real-time polarization resistance R in 4 surfaces for testP is real-timeAnd solution is electric in real time
Hinder RSol is real-timeRevised real-time anode polarization resistance, real-time anode polarization resistance R just can be obtainedP is real-time"=(RP is real-time-RSol is real-time)/2,
Since B values have obtained, the real-time corrosion rate I in metal surface can be directly obtained according to Stern formulaCorr is real-time=B/
RP is real-time”。
Claims (8)
1. a kind of corrosive pipeline rate on-Line Monitor Device, it is characterised in that：Be included in Monitoring Pinpelines position it is front and back be arranged
Line monitoring device inlet ball valve (1) and on-Line Monitor Device vent ball valve (10), on-Line Monitor Device inlet ball valve (1) downstream
It is provided with flowmeter (2) on pipeline, bipolar electrode electro-chemical test electrode clamping device is provided on the pipeline in flowmeter (2) downstream
(3) bipolar electrode (4) for test of clamping, the pipeline in bipolar electrode (4) downstream for test divide two-way, are set on pipeline all the way
Be equipped with hanger device inlet ball valve (7) and hanger device (8), be provided on another way pipeline hanger device bypass ball valve (6), two
It is provided with on-Line Monitor Device vent ball valve (10) on pipeline after the pipeline merging of road；Further include and the bipolar electrode for test
(4) connected Electrochemical Comprehensive Tester (5), the corrosion coupon (9) being arranged in hanger device (8).
2. corrosive pipeline rate on-Line Monitor Device according to claim 1, it is characterised in that：The bipolar electrode electrochemistry
Test electrode clamping device (3) is process for organic glass, and internal is the channel of rectangle, in the symmetrical side wall of rectangular channel
Tapping is equipped with the opposite bipolar electrode (4) for test, tapping tapping thread, the clamping of bipolar electrode electro-chemical test electrode
Standard size of flange is processed at device both ends, is bolted with the flange welded on pipeline.
3. corrosive pipeline rate on-Line Monitor Device according to claim 2, it is characterised in that：Pair for test
Electrode (4) is that polytetrafluoro bar (11) is process with metal bar (12), embedded among polytetrafluoro bar (11) and monitoring
The metal bar (12) of pipeline same material, polytetrafluoro bar (11) one end external threading, with bipolar electrode electro-chemical test electrode
Clamping device (3) internal thread matches, and the other end is processed as hexagon, facilitates and metallic rod is fastened and drawn with spanner conveniently
It is connect with Electrochemical Comprehensive Tester (5).
4. corrosive pipeline rate on-Line Monitor Device according to claim 1, it is characterised in that：The hanger device (8)
It is process for organic glass, inside is circular channel, channel cross-sectional area and bipolar electrode electro-chemical test electrode clamping device (3)
Inner passage sectional area it is identical, standard size of flange is processed at both ends, convenient to be connected by bolt with the flange welded on pipeline
It connects；
The corrosion coupon (9) is standard test piece identical with pipe material, and the punching of test piece both ends is connected and fixed by fishing line
In hanger device (8).
5. the on-line monitoring method of Claims 1-4 any one of them corrosive pipeline rate on-Line Monitor Device, feature exist
In：Include the following steps：
Step 1, according to corrosive pipeline monitor position it needs to be determined that the position of corrosive pipeline on-Line Monitor Device, according in pipeline
The medium flow direction short circuit that forward and backward opening is welded the primary door of import and export and extended near Monitoring Pinpelines position, corrodes online prison
Device is surveyed to be welded to connect with short circuit by on-Line Monitor Device inlet ball valve (1) and on-Line Monitor Device vent ball valve (10)；
Step 2, the liquid in pipeline passes sequentially through on-line corrosion monitoring device inlet ball valve (1), flowmeter (2), bipolar electrode electricity
Test chemical electrode clamping device (3) and electrode (4) for test, electrode (4) are connected with Electrochemical Comprehensive Tester (5)
It connects, then, liquid is by hanger device inlet ball valve (7), hanger device (8) and corrosion coupon (9) or directly passes through lacing film
Device bypass ball valve (6) is most returned to through on-Line Monitor Device vent ball valve (10) in monitoring pipeline afterwards；
Step 3, open on-Line Monitor Device vent ball valve (10), close hanger device bypass ball valve (6), open hanger device into
Mouth ball valve (7) is controlled by adjusting the aperture of on-Line Monitor Device inlet ball valve (1) through bipolar electrode electro-chemical test electrode
The flow velocity of clamping device (3) and hanger device (8) is consistent with the flow velocity of solution in institute monitoring pipeline, runs 3 days, passes through electrochemistry
Comprehensive tester (5) is measured every 4h for the solution resistance R between the bipolar electrode (4) of testsol, measure a pair every 4h and be used for
Linear polarization resistance R between the bipolar electrode (4) of testp, take the average value R of linear polarization resistance in 3 daysP is flatAnd solution resistance is flat
Mean value RSol is flat, with the average value R of linear polarization resistanceP is flatSubtract the average value R of solution resistanceSol is flat, obtain excluding solution resistance shadow
Loud electrode polarization resistance Rp', with the electrode polarization resistance R for excluding solution resistance influencep' divided by 2 obtain anode polarization resistance
Rp", the corrosion coupon (9) in hanger device (8) is taken out, corrosion coupon (9) surface corrosion product is cleaned out, passes through weight-loss method
Calculate the corrosion rate I of corrosion coupon (9)Corr is weightless, B=I is obtained according to Stern formulaCorr is weightless·Rp”；
Step 4, open on-Line Monitor Device vent ball valve (10), open hanger device bypass ball valve (6), close hanger device into
Mouth ball valve (7) controls the stream by electrode clamping device (3) by adjusting the aperture of on-Line Monitor Device inlet ball valve (1)
Speed is consistent with the flow velocity of solution in institute monitoring pipeline, measures the real-time polarization resistance R in bipolar electrode (4) surface for testingP is real-time
And real-time solution resistance RSol is real-time, with real-time polarization resistance RP is real-timeSubtract real-time solution resistance RSol is real-time, obtain excluding molten
The real-time electrode polarization resistance R of liquid Resistance InfluenceP is real-time', with the real-time electrode polarization resistance for excluding solution resistance influence
RP is real-time' divided by 2 obtain real-time anode polarization resistance RP is real-time", it is directly obtained according to Stern formula by the B values obtained in step 3
The monitored real-time corrosion rate I in metallic conduit surfaceCorr is real-time=B/RP is real-time”。
6. on-line monitoring method according to claim 5, it is characterised in that：Corrosive pipeline described in step 1 monitors position
It sets and chooses the maximum position of flow velocity in pipeline；The primary door of import and export described in step 1 and the short circuit that extends are in equipment out of use
Period is welded in time after draining the solution in pipeline, facilitates the installation of subsequent corrosion on-line monitoring equipment.
7. on-line monitoring method according to claim 5, it is characterised in that：Bipolar electrode in the step 3 for test
(4) the solution resistance R betweensolMeasurement use galvanostatic charge curve methodology, in 0s~5s for being applied between the bipolar electrode of test (4)
With step current IsolAnd record the value E of voltage between bipolar electrodesol, the resistance when the time is 0s is solution resistance Rsol=
Esol/Isol；
For the linear polarization resistance R between the bipolar electrode (4) of test in the step 3pMeasurement, using linear polarization method, scanning
Ranging from relative to open circuit potential ± 10mV, sweep speed 20mV/min, linear polarization resistance R between the bipolar electrodepFor electrode
Polarization resistance Rp' and solution resistance RsolSum, thus be excluded that solution resistance influence electrode polarization resistance Rp'=Rp-Rsol；
The step 3 Anodic polarization resistance Rp" measurement, since two-electrode system does not have reference electrode, when impressed current passes through
When anode and cathode, anode potential deviates equilibrium potential to shuffling, and cathode potential deviates equilibrium potential to negative shifting, and the two is simultaneously
It carries out, absolute value is equal；Polarization potential under the conditions of this is potential difference △ E of the anode relative to cathode, at this time △ E=△
ESun-△EIt is cloudy, since cathodic polarization potential is negative value, so △ E=△ ESun+|△EIt is cloudy|=2 × △ ESun, △ ESun=△ E/2, online
Property polarized area polarization potential and polarization resistance be linear relationship, therefore anode polarization resistance Rp"=Rp'/2。
8. on-line monitoring method according to claim 5, it is characterised in that：Stern formula I in the step 3corr=
B/Rp, B is Stern constant, is constant constant under certain monitoring of environmental.
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| CN109632617A (en) * | 2018-12-25 | 2019-04-16 | 中国航空工业集团公司北京长城航空测控技术研究所 | A kind of method of real-time monitoring corrosion of aluminium alloy rate |
| CN109946221A (en) * | 2019-03-22 | 2019-06-28 | 夸克能源工程实验室(深圳)有限公司 | A kind of hanger device for evaluating pipeline corrosion and cathodic protection effect |
| CN110274993A (en) * | 2019-06-18 | 2019-09-24 | 中国石油天然气股份有限公司 | A kind of online corrosion evaluating device |
| CN110410677A (en) * | 2019-06-18 | 2019-11-05 | 中国石油天然气股份有限公司 | A kind of online fouling evaluating apparatus |
| CN111141670A (en) * | 2020-01-14 | 2020-05-12 | 中国科学院上海应用物理研究所 | On-line monitoring and regulating method for chloride molten salt corrosion |
| CN111398157A (en) * | 2020-04-15 | 2020-07-10 | 中国船舶重工集团公司第七二五研究所 | Small-caliber copper alloy pipeline polarization resistance testing device and method |
| CN115575308A (en) * | 2022-08-25 | 2023-01-06 | 哈尔滨工业大学 | Electrochemical corrosion device and test method for FRP reinforced defective pipeline |
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