Cathodic protection is widely used to prevent the corrosion of metal structures immersed in electrolytes and buried pipelines. Coupled multielectrode array sensors (CMAS) (see U.S. Pat. Nos. 6,683,463, 6,132,593, and 7,180,309) have been used for corrosion monitoring for cathodically protected systems [see X. Sun, “Corrosion monitoring under cathodic protection (CP) conditions using multielectrode array sensors,” in “Corrosion Monitoring Techniques,” L. Yang, ed., Woodhead Publishing, Success, UK (2008), Chapter 26, and pages 614 to 637]. However, the evaluation of the effectiveness of CP with the coupled multielectrode array sensors (CMAS) is by using the measured corrosion rate or corrosion current under the same CP conditions applied to the metal structures and pipelines. The corrosion rate decreases from a large value to zero and is an effective parameter for showing the effectiveness of CP when the CP changes from being ineffective to being just adequate to stop the corrosion. However, the corrosion rate remains zero and cannot be used to indicate the degree of CP when the CP changes from being just adequate to being excessive. Excessive CP should be avoided because it causes significant evolution of hydrogen which causes adverse effect such as the disbanding of the protective coatings on the metal or hydrogen embrittlement of the metal. To date, there is not a parameter from the CMAS probe that can be used to evaluate the effectiveness of CP when the when CP operates under the desired conditions. The CMAS probe cannot be used to control the CP systems to operate within the optimum range of conditions.
This invention is related to a method on how to control and monitor the CP for immersed metal structures and buried pipeline so that it operates in the desired range between being adequate and being excessive by using parameters from a multielectrode electrochemical sensor. This method does not need a reference electrode which requires periodical service and has a limited service life.
Cathodic protection (CP) control has been relying on the measurements of structure-to-electrolyte potentials. The commonly accepted criterion for controlling CP is that the instant-off structure-to-electrolyte potential is within a certain range so that the CP is adequate but not excessive. For example, the instant-off potential should be between −0.85 and −1.2 V vs Cu/CuSO4 (VCSE) for pipelines buried in soil. However, the measurement of such potentials requires a reference electrode which usually contains a liquid electrolyte and requires periodical maintenance and has a limited service life, especially under wet and dry conditions. In addition, the effective range of potentials varies somewhat with temperature and pH of the surrounding soil. Corrosion may occur even within the specified range. This invention enables the evaluate the effectiveness of CP without the need to measure the potential and eliminate errors associated with the reference electrodes and the uncertainties of using the potential to evaluate the effectiveness of the CP.
5 sensing surface of multielectrode probe (15) viewed from the lower end of the probe
10 individual electrodes on the sensing surface exposed to the corrosive electrolyte (soil for example)
10
a electrodes that are made from a type of metal
10
b electrodes that are made from another type of metal
10
c electrodes that are made from a metal that is further different from 10a and 10b
15 multielectrode probe (or coupled multielectrode array sensor probe)
20 electrical cable of probe
25 electrical wires connecting each individual electrode to a current-measuring device (35)
30 multielectrode instrument
31 multielectrode instrument for CP Control
35 multi-channel ammeter in the multielectrode instrument
40 coupling joint where all wires from individual electrodes are joined
45 wire connecting the coupling joint (40) to the buried pipe or immersed metal (65) under cathodic protection
50 test station for buried pipe or metal structures where the access to the electrical cables (55) that are connected to the buried pipe or immersed metal structure (65) are available
5 electrical cable connected to the buried pipe or immersed metal structures (65)
60 point where the electrical cable (55) is electrically jointed to the buried pipe or metal structure (65)
65 buried pipe or immersed metal structure in contact with the corrosive electrolyte or soil (70).
70 electrolyte that causes corrosion (soil for example)
75 rectifier that provides the CP for the buried pipe or immersed metal in the case of the impressed current cathodic protection systems
80 anode that is buried in the soil or immersed in the electrolyte surrounding the metal
In practice, CP is usually applied such that the metal structure is slightly over protected (with the CP potential slightly lower than the critical protection potential) to guarantee that there is a safe margin of the protection, but not excessive protection which may cause significant evolution of hydrogen and damage to the coatings on the metals as well as hydrogen embrittlement. Since the minimum corrosion rate is zero (corrosion rate cannot be negative) and, to date, there has not been a way to represent the safe margin of the CP for the CMAS probe.
This invention discloses a method on how to use the currents measured from a multielectrode sensor for monitoring the effectiveness to cathodic protection and control the cathodic protection within the optimum range.
Before the application of the CP, the potential of the coupling joint was at the free corrosion potential. At the corrosion potential, some electrodes were anodes and some electrodes were cathodes and the current from the most anodic electrode (Iamax) represented the maximum corrosion current on the multielectrode sensor. After the CP was applied, all of the currents started to decrease and the Iamax reached zero when the CP potential reached the minimum adequate CP potential. When the Iamax reached zero, the metal was fully protected because the most anodic electrode (which represents the most vulnerable corrosion site of the metal) is protected.
As the CP potential further decreased, both Icmax and the Iamax became more and more negative. When the CP potential reached another critical value (the excessive CP potential), Icmax jumped to a large negative value which usually indicates that significant hydrogen evolution started on the most cathodic electrode. This large negative value is called the maximum allowable CP current (ICP_limit) because it corresponds to the excessive hydrogen evolution (see the section for
The current from the most anodic electrode and the current from the most cathodic electrode may also be represented by the values derived using statistic methods for more reliable results. Such values are called the statistical most anodic current (Iamax,stat) and the statistical most cathodic current (Icmax,stat). For example, the statistical most anodic current may be derived by using the sum of the average of all the currents from the multiple electrodes (AVG) and the standard deviation (STD) of all the currents times a factor (k):
I
a
max,sta=AVG+k×STD
where k is a positive number from 0.5 to 5.
Similarly, the statistical most cathodic current may be derived by using the difference between the average of all the currents from the multiple electrodes (AVG) and the standard deviation (STD) of all the currents times the factor:
I
c
max,stat=AVG−k×STD
When the Iamax,stat reached zero, the metal was fully protected because the statistical most anodic current statistically represents the corrosion current from the most vulnerable corrosion site of the metal. When the Icmax,stat reached the maximum allowable value, statistically, there is excessive hydrogen evolution at one of the sites on the metal. The CP potential controlled between the minimum adequate CP potential and the excessive CP potential as shown in
Responses of the CP effectiveness margin (CPEM) to the CP potential. Note: the CPEM was calculated with the current from the statistical most anodic electrode. The CPEMc was calculated with the current from the statistical most cathodic electrode and its value of 100% corresponds to the Excessive CPEM.
The CPEMc in
Alternatively, a much easier method may be used to obtain the approximate value of the maximum allowable current. This easier method requires only the measurement of the current from the multielectrode probe or a coupon made of the same metal as the electrode of the probe while polarize the probe or the coupon to the maximum allowable CP potential specified in a relevant standard (e.g. −1.2 VCSE). The current density derived from the current measured at the threshold excessive CP potential can be used as the maximum allowable current density or the maximum allowable current after the electrode surface area is accounted for.
After more data in the different soil or electrolyte environments are available, the maximum allowable current can be estimated.
The maximum allowable CP current can also be arbitrarily set to the negative of the current from the most anodic electrode times a factor between 1 and 10 before cathodic protection is applied. The maximum allowable CP current can also be arbitrarily set to the current from the most cathodic electrode times a factor between 1 and 10 before cathodic protection is applied.
Alternatively, the multielectrode instrument for CP control (31) has the capability to derive the above-mentioned CPEM and control the rectifier's outputs such that the CPEM is between 0 and the excessive CPEM. If it is not practical to control the CPEM to be between 0 and the excessive CPEM, The CPEM should at least be control between 0 and 100%.
In a coupled multielectrode array sensor (CMAS), the electrodes are usually made of the same metal that represents the pipe wall or the metal structure whose corrosion rate is being measured. In this case, the variations of the measured currents from the CMAS (some small and some large and some are anodic and some are cathodic) reflect the variations of the microstructure of the pipe wall or metal structure being measured and also the variations of the local chemistry in contact with the metal surface.
In addition, for legacy pipelines, especially those that have been repaired, or that have sections being replaced, the pipeline that is under the same CP protection system is actually consisted of different metals. The multielectrode sensor as shown in
In the above discussion, the denominator used to derive the degree of cathodic protection or CPEM is the maximum allowable CP current which is predetermined based on the extrapolation of the hydrogen evolution curve or measurement of current when the electrode are polarized to the threshold CP potential. This value may be replaced by a more easily obtainable value such as the Iamax, or Icmax, before or after CP as shown in
The method described are mainly for monitoring the degree of cathodic protection of pipes buried in soil and metal structures immersed in electrolyte solutions. The method may also be used in other systems and environments.
Although the present invention has been described in detail, it should be understood that various changes, substitutions, and alterations can be made hereto, without departing from the spirit and scope of the invention as defined by the appended claims.
Accordingly, the method disclosed in this invention new parameter uses the current form the most anodic electrode and the current from the most cathodic electrode from a multielectrode sensor, or the ratio of such currents to a large cathodic value, called the maximum allowable for CP control. This ratio is called the cathodic protection effectiveness margin (CPEM). It allows the operator to safely control the CP without using a reference electrode. When the CP is insufficient, the CPEM is less than zero; when the CP is sufficient, the CPEM is between 0 and 100%. The value of 0% means that the system is just barely protected, while the value of 100% means that the CP starts to be excessive. Therefore, the CPEM is an effective parameter for monitoring and controlling the CP.
Compared with the commonly adopted instant-off potential criteria, the method disclosed in this invention does not require a reference electrode. As the multielectrode probe is consisted of only metal electrodes and solid insulators, it is maintenance free and its service life may be the same as the protected structures. In addition, the multielectrode probe also provide the quantitative information on the degree of corrosion damage when the CP is insufficient.
This application is the re-submission of a previous application (application Ser. No. 16/602,142) filed 2019 Aug. 12 by the first inventor of the present invention. The previous application was considered abandoned due to the failure to respond to a Notice to File Missing Parts which the applicant did not receive. The applicant had submitted a petition request to withdraw the holding of abandonment and is waiting for the decision on whether the petition will be granted. Applicants resubmit the present application, in case, the applicant's petition is not granted. In the present application, some errors in the previous application have corrected and some paragraphs and claims have been amended, as a result, the second inventor's name has been added to the present application. In case the applicant's petition is granted, applicants will withdraw the claims in the present application that overlaps with those in the previous application.