Patent Application
20190048477
Embodiments of the present invention relate generally to cathodic protection of metallic objects subjected to corrosion. More precisely, embodiments of the invention relate to a system and a method for cathodic protection by deposition of protective sacrificial coatings onto the surface of a metallic, ferrous or non-ferrous, object. In analogy, herewith embodiments of the invention also relate to a subsea component carrying the cathodic protection system of embodiments of the present invention.
The system and method of embodiments of the present invention drastically reduces the total cathode area by distributing the sacrificial anode over the structure to be protected, yet providing an equivalent degree of protection to that of conventional sacrificial anodes. Embodiments of the invention, hereafter also named cathodic protection by distributed sacrificial anodes (DSA), can effectively reduce the total cathode area entirely, or reduce the same to small defects accounting for a small fraction of the total surface area of the component, or be used in combination with conventional sacrificial anodes in case larger areas have to be traditionally coated, e.g. paint systems and other non-conductive coatings.
Electrochemical corrosion is a process that is initiated when an electrically conductive metal structure gets in contact with an electrically conductive substance, such as wet soil or water which can contain various oxidants. In subsea systems, seawater acts as the electrolyte of a galvanic cell in which a current passes from an anode site to a cathode site of a submerged metal structure, causing electrochemical changes that result in corrosion products in the metal. During uniform dissolution of a ferrous metal structure submerged in seawater, e.g., positively charged iron ions (Fe2+) are released into water from the anode site while the freed electrons (e−) move to the cathode site in the surface of the metal. At the cathode site a reduction reaction takes place in which the electrons are transferred to dissolved oxygen (O2) and water (H2O) to form hydroxide ions (OH+) and hydrogen, depending on the pH and temperature of the electrolyte. Ferrous ions combine with hydroxide ions to form iron hydroxide (Fe(OH)2), or rust. If no measure is taken to prevent electrochemical corrosion the entire structure may be affected. Non-ferrous metals react in a similar way forming different types of corrosion products.
In the absence of a preventive measure, for example, cathodic protection, the portion of the structure that has the lowest free corrosion potential will be subject to active dissolution.
Cathodic protection is a method to combat corrosion in which the structure to be protected is made the net cathode in a galvanic cell. When properly designed, a cathodic protection system can reduce corrosion rates by more than 2 orders of magnitude or supress corrosion entirely.
In sacrificial cathodic protection, an active metal, i.e. a metal or alloy that has a free corrosion potential that is lower than that of the structure to be protected, is electrically connected to the structure. In this electric circuit, the metal with the lowest (i.e. the more negative) free corrosion potential becomes the net anode, while the structure becomes the net cathode. Corrosion of the more active metal polarizes the structure to potentials below its free corrosion potential, reducing or supressing corrosion depending on the coupled potential. In subsea applications, e.g., the typical cathodic protection potential by sacrificial aluminium-based anodes is in the order of −1.1 to −1.0 V vs. Ag/AgCl|seawater. Nevertheless, as a rule of thumb, a structure is considered protected against corrosion when it is polarized below −0.8 V vs. Ag/AgCl|seawater.
Sacrificial anodes are made of metals and alloys that will readily corrode in the given environment. Metals that are anodic to most engineering alloys used in subsea oil and gas production are based on aluminium and zinc, which can be used as sacrificial anodes in substantially pure form or as alloys. Today, the oil and gas industry has standardized in the Al-Zn-In system, whereas the use of Zn-based anodes is discouraged due to passivation and polarity reversal in seawater.
Sacrificial cathodic protection of submerged equipment in subsea oil and gas production and transport often requires some considerable anode mass to protect remote subsea components. Anode demand is traditionally determined by international standards such as DNV RP B401 (Det Norske Veritas' recommended practice) and ISO 12473. A total anode mass in the order of several tens of tonnes is not unusual for a subsea oil and gas system. The total tonnage of the CP system adds to the total weight and complexity of the structures, adding considerable installation, operation, and maintenance costs.
In the past, several attempts have been made to avoid the need for great anode masses to achieve corrosion protection of buried or submerged equipment. One strategy which has several followers in the literature is the application of thin coatings onto the exterior of an object that needs protection.
One example of this strategy can be found in US 2015/226365 A1. In embodiments of this invention, an iron-based piping element is coated with an inner layer that is anodic to the iron base. An outer layer about 1-5 mm thick is made of polyethylene or polypropylene resin. The outer layer provides a dielectric sealant on top of the inner layer.
Another example from the same strategy can be found in CN 2536879. An oil pipe is coated with an inner layer that is anodic to the pipe base. The inner layer is protected by a top layer made of epoxy resin and is dielectric.
A similar approach can be found in CN 201187267 which discloses a multilayer variant of anticorrosive protection by coatings. A first passivating layer of duplex stainless steel is applied to the exterior of an oil or gas pipe. A second layer 100-150 μm thick is applied to the first layer, the second layer being anodic to the first layer and pipe base. A 10-50 μm thick sealant is applied as top coating.
Another multilayer coating system is disclosed in U.S. Pat. No. 8,697,251 B2. A metal substrate is coated with an inner layer, an outer layer and an intermediate layer. The inner layer is anodic to the metal substrate. The intermediate layer is anodic to one or both of the substrate and the inner layer. The outer layer is an oxide and functions as a dielectric coating thus preventing electrochemical contact between the underlying layers and the surroundings. Aluminium oxide (Al2O3) is mentioned as a suitable dielectric in the outer layer of the multilayer coating system. The total thickness of the system amounts to about 250 μm, whereas the thickness of the intermediate layer, functioning as sacrificial anode, is about 50-75 μm.
A problem in multilayer coating systems such as the one disclosed in U.S. Pat. No. 8,697,251 B2 is that corrosion of an underlying layer can cause blistering and separation between layers. This problem arises when the surface of a lower layer corrodes and corrosion products are formed. The corrosion products have poor mechanical properties and are typically subject to swelling, which can be due to the formation of hydrates or due to the corrosion products being soluble in water. An additional complication is that the external layer of these systems, i.e., the one exposed to the corrosive fluid, is either a dielectric or an electric insulator. Thus, the solutions as mentioned above primarily rely on the integrity of the barrier coating. If forming part of a subsea system, those areas must be taken into consideration in the cathodic protection design.
In general terms, embodiments of the present invention reduce or suppress anode consumption by reducing or eliminating the total cathode area to be protected. Embodiments of the invention drastically reduce anode mass while maintaining a degree of corrosion protection identical to that of CP by conventional Al-based sacrificial anodes (e.g., stand-off, flush-mount or bracelet anodes).
An object of the present invention is to provide a cathodic protection system for corrosion protection of a ferrous or non-ferrous metal substrate.
This object is met by a system as defined in appended system claims.
Another object of the present invention is to provide a method for applying cathodic protection to a ferrous or non-ferrous metal substrate.
This object is met by a method defined in appended method claims.
Still another object of the present invention is to provide a corrosion resistant subsea component intended for transport of hydrocarbon fluid via a lumen or passage through a body made of ferrous or non-ferrous metal.
This object is met by a component defined in appended component claims.
Thus, in a first aspect, the present invention is a cathodic protection system for a metal component or substrate comprising:
a metallic first-layer coating which is anodic to the substrate, bonded to the component or substrate and electrically conductive,
a sacrificial anode in the form of a metallic second-layer coating distributed over the first-layer coating, the second layer coating having an open circuit potential that is equal to the metallic first-layer coating or being anodic to the first-layer coating, the second-layer coating electrically conductive, bonded to the first-layer coating and exposed to the surrounding environment.
An essential aspect of the second-layer coating that is exposed to the environment is that it matches the electrochemical properties (i.e. free corrosion potential and current capacity) of a conventional sacrificial anode which is replaced in full or in part by the second-layer coating. The second-layer coating functions as sacrificial anode supplying current to defects or uncovered areas or adjacent structures, as appropriate.
Since the sacrificial anode is distributed over the structure, the total cathode area is reduced or eliminated.
Distributing the anode also reduces problems associated with Ohmic drop, and improves current distribution.
Defects in the second-layer coating that could potentially lead to exposure of the underlying first-layer coating or the substrate, such as mechanically caused defects induced during handling or installation, e.g., can be assumed to be limited to small portions of the entire protected area. A total maximum of, e.g., one percent (1%) defect area in the outer coating is a moderate prediction, yet illustrating the potential benefit achievable by reducing the cathode area.
Because embodiments of the proposed invention reduce total cathode area by distributing the sacrificial anode over the entire structure to be protected, the saving in total anode mass is substantial. The reduction in anode by virtue of the proposed CP by DSA is illustrated by the following comparative example:
A planned pipeline end termination (PLET) assembly for an eight well, three manifold scheme of a gas field development situated some 130 km off the shore at a tropic/sub-tropic water depth of approximately 200 m would require a calculated gross mass of conventional anodes of approximately 26,000 kg in sacrificial cathodic protection designs when following the DNV-RP-B401 guidelines.
With an assumed defect area of 1% in the DSA the same components would need a total conventional anode mass of approximately 2,000 kg, equaling a weight reduction of conventional anodes of about 92%. The reduction in conventional anode mass equals about 20% of the total weight of the PLET.
The first-layer coating contains essentially pure metallic aluminium or aluminium alloy. The choice of aluminium for the first-layer coating results in reduced demand for sacrificial anode mass as compared to the anode demand required to protect a bare metallic component or substrate.
Likewise, the second-layer coating is made of an aluminium alloy that has identical open circuit potential or being anodic to the first-layer coating. The second-layer coating is also anodic to the component or substrate.
The chemical composition of the second-layer coating exposed to the environment, in an embodiment, matches that of a conventional sacrificial anode, which is replaced in full or in part by the sacrificial second-layer coating.
The surface exposed to the environment shall, in an embodiment, be made of an aluminium-zinc-indium (Al-Zn-In) alloy or other aluminium alloy with electrochemical properties matching those of the Al-Zn-In alloy.
The second-layer coating may be an Al alloy comprising Zn in the range of 2-7% and In in the range of 0.01-0.05%.
The first-layer coating, in an embodiment, has a thickness in the range of 100-300 μm. The second-layer coating, in an embodiment, has a thickness in the range of 200-3,000 μm, more particularly, at least more than 200 μm, and more particularly from 300 to 1,500 μm.
The thickness of the second-layer coating that is exposed to the environment will be determined based on the self-corrosion rate of the component or substrate and the required minimum thickness by the end of the service life of the component. Based on the results of internal research activities, a thickness of 50 μm per 10 years of service is a conservative value for the PLET example discussed above.
The second-layer coating is distributed over essentially the entire surface of the inner coating.
The first-layer and second-layer coatings are, in an embodiment, distributed over essentially the entire area of the component or substrate that is exposed to a corrosive environment, or to the maximum extent practically possible.
In a second aspect, the present invention is a method for cathodic protection of a metallic component or substrate, the method comprising:
applying a metallic first-layer coating that being anodic to the component or substrate through a first deposition method,
distribution of sacrificial anode over the first-layer coating by applying a metallic second layer coating that has open circuit potential equal to the metallic first-layer coating or being anodic to the first-layer coating through a second deposition method.
The first and second deposition methods can be chosen from deposition methods such as hot dip galvanization, co-lamination, co-extrusion, and explosion bonding, as well as any deposition method referred to as metal spraying including but not limited to one of detonation spraying, flame spraying, high-velocity liquid fuel spraying, high-velocity air fuel spraying, high-velocity oxygen fuel spraying, plasma spraying, arc spraying and cold spraying, the first and second deposition methods being the same or different from each other.
Embodiments of the method comprise deposition of essentially pure metallic aluminium or aluminium alloy to a thickness of 100-300 μm to form the first-layer coating of the component or substrate.
Embodiments of the method further comprise deposition of metallic aluminium alloy that has open circuit potential equal to the metallic first-layer coating or is anodic to the metallic first-layer coating to form a second-layer coating having a thickness in the range of 200-3,000 μm, more particularly at least more than 200 μm, and more particularly from 300 to 1,500 μm.
In an embodiment, the method comprises feeding a metallic composition comprising aluminium, zinc, and indium to a metal deposition process for deposition of a sacrificial anode coating onto the first-layer coating.
In a third aspect, the present invention is a component designed for subsea use made of ferrous or non-ferrous metal, wherein in submerged state the component is at least partly exposed to seawater. On at least the exposed surface thereof the component is applied
a first-layer coating consisting of essentially pure aluminium or aluminium alloy, the first-layer coating shielded from seawater by
a second-layer coating in contact with seawater, the second-layer coating containing aluminium alloy being anodic to aluminium and to the component.
The component may be designed for transport of hydrocarbon fluid via a lumen or passage through a body made of ferrous or non-ferrous metal,
The component may be covered by a sacrificial anode coating containing an aluminium-zinc-indium (Al-Zn-In) alloy.
In accordance with the aforesaid, the sacrificial anode covering the component has a thickness in the range of 200-3,000 μm, more particularly at least more than 200 μm, and more particularly from 300 to 1,500 μm. The first-layer coating, in an embodiment, has a thickness of 100-300 μm.
Without exclusion of others not mentioned, the component can be realized at least as one of the following subsea components:
trees
blow out preventers
tools
pipelines
flowlines
jumpers
manifolds
connectors and connections
pressure vessels
housings and hulls
pumps or compressor parts
valves
flow meters
sensors
control system modules
umbilicals and associated termination assemblies
risers and riser bases
suction anchors and mud mats
support structures and connections therefor.
Embodiments of the invention can be applied to components used for oil or gas related equipment, but also e.g. for wind mills, fish farming facilities, any cable or pipeline structure at least partly submerged in seawater, ships and vessels, etc.
In accordance with the specifications of the cathodic protection system and method described above the component is covered by a distributed sacrificial anode mass containing an aluminium-zinc-indium alloy, or other aluminium alloy with corresponding electrochemical properties.
Embodiments of the invention will be further explained below with reference made to the accompanying, schematic drawings. In the drawings
The use of protective coatings is not exclusively applicable to subsea structures, but applies generally also to buried pipelines or in protection against atmospheric exposure.
It shall also be noted, that if not otherwise stated, any statement on percentage of constituents given herein refers to percentage by weight.
In subsea cathodic protection CP, codes like DNV-RP-B401 establish coating degradation factors to account for the normal aging process of different coating systems. While initial coating breakdown factors are typically small, they approach a value of 1 by the end of the service life of the substructure.
In subsea CP design, the entire surface area of the component must be accounted for in CP calculations because it is cathodic to the conventional anodes. Conversely, surface areas of the structure that have an open circuit potential identical to that of the conventional sacrificial anodes will not be included in the CP calculations.
In
The substrate 1 can be an object of any ferrous or non-ferrous metal that needs either protection from a corrosive environment such as wet soil, water and moist air, or an object which has to be covered to reduce the total anode consumption of a CP system. In subsea applications, the substrate would typically be a component involved in the subsea production and/or transport of oil, gas or water, such as a pipeline, a manifold structure, a pump or compressor part etc., typically having a lumen or passage 4 for transport of fluid through a body of metal 1. The substrate 1 can thus in practise take any form including planar, curved and double-curved shapes, and the coated surface of the substrate can be situated on the exterior or on the interior of the substrate.
The first-layer coating 2 may comprise any metal or metal alloy that is anodic to the substrate, is electrically conductive and can form a bond to the substrate. The second-layer coating 3 may comprise any metal or metal alloy that has an open circuit potential equal to the metallic first-layer coating or is anodic to the first-layer coating and the substrate, is electrically conductive and which can form a mechanical bond to the first-layer coating. In all cases the metals or metal alloys of the first- and second-layer coatings shall be related in the galvanic series such that the second-layer coating 3 forms a sacrificial anode for the first-layer coating 2 or the substrate, and the first-layer coating shall never be anodic to the second-layer coating
In embodiments, the first-layer coating 2 contains essentially pure metallic aluminium or aluminium alloy. Pure aluminium or aluminium alloy is, in an embodiment, in this case to reduce the anode demand when compared to the anode demand required to protect the substrate. The pureness of the first-layer coating may be in the range of 85-100% Al. The first-layer coating may alternatively be an aluminium alloy. In embodiments, the first-layer coating 2 contains 99.5% Al, or an Al-alloy containing 5% magnesium (Al5Mg).
Aluminium alloy anodic to pure aluminium and to the substrate is preferred as the second-layer coating 3. A composition in the second-layer coating 3 is an aluminium-zinc-indium (Al-Zn-In) alloy, although other aluminium compositions that provide corresponding electrochemical properties may constitute an alternative. Other substances that can be combined with aluminium beside zinc and indium in the sacrificial second-layer coating 3 are for example cadmium (Cd), silicon (Si), tin (Sn), manganese (Mn) and titanium (Ti).
In a Al-Zn-In alloy the zinc may constitute about 2-7% of the composition, indium may amount to about 0.01-0.05%, whereas aluminium constitutes the balance. As will be understood from the aforesaid the composition of the second-layer coating 3 may be similar to that of conventional sacrificial aluminium anodes used to protect subsea components.
Application of the first- and second-layer coatings to the substrate may include any suitable application process such as co-lamination, co-extrusion and explosion bonding, e.g., wherever this can be permitted with respect to the design of the substrate, such as in connection with planar plates, pipes and rods of continuous radius. For more complicated shapes, metal spraying is the method for deposition of both the first-layer coating 2 and the second-layer coating 3.
Metal spraying is a general name for several processes in which pure or alloyed metal is melted in a flame or arc and sprayed onto a substrate by means of compressed air or explosion gases. Micrometre-sized droplets of metal are this way created and projected towards the surface of the substrate. By repeating the process, droplets will successively accumulate to form a coating.
Under the general concept of metal spraying several variations which are suitable for deposition of the first- and second-layer coatings 2 and 3 can be distinguished, such as plasma spraying, detonation spraying, wire arc spraying, flame spraying, high velocity oxy-fuel spraying, warm spraying or hot spraying, cold spraying, e.g.
A key feature in embodiments of the present invention is the provision of a sacrificial anode coating 3 which is distributed over essentially the entire area of the substrate/component that is exposed to a corrosive environment. The thickness of the second-layer coating 3 is determined by the self-corrosion rate over the service life of the component, whereas the total thickness is a function of the estimated current demand to protect any defect area(s) in the second-layer coating.
It is assumed that the Al-Zn-In anode composition in the second-layer coating 3 of the embodiment is favoured by a uniform corrosion which affects and reduces the need for layer thickness. A layer thickness in the range of 300-1,500 μm is well within the capacity of metal spraying methods. The range will also cover most applications in terms of service life and operational conditions. It is however within the scope of embodiments of the invention to increase the layer thickness of the second-layer coating 3 up to about 3,000 μm if required, whereas above that range the benefit of weight reduction as compared to fitting of conventional anodes will be less obvious. In any case, the thickness of the second-layer coating 3 should not be less than 200 μm.
As already has been stated in other parts of the disclosure the thickness of the inner coating 2 is, in an embodiment, within 100-300 μm.
From the above specification of the cathodic protection system it is appreciated that the second-layer coating 3 constitutes a sacrificial anode mass which is distributed over the substrate and protected component, and which is in direct contact with the environment that surrounds the component. The predominant material in both the first- and second-layer coatings is metallic aluminium which provides electrical conductivity and good bonding properties between the coatings themselves and towards a substrate of ferrous metal and of non-ferrous metal as well.
The distributed sacrificial anode of the second-layer coating may also be used in combination with conventional sacrificial anodes in case larger areas have to be traditionally coated, e.g. through paint systems or other non-conductive coatings. In all cases embodiments of the invention as claimed provide substantial reduction in anode mass and weight whenever applied in a structure that is subjected to a corrosive environment.
Conclusively,
For the experiments, samples designated DSA were prepared by first applying Al-Zn-In-alloy to carbon steel panels by thermal spraying, then samples were cut to size and finally prepared for electrochemical testing by effectively sealing off all carbon steel surfaces of the sample, leaving DSA as the only metallic part of the samples being exposed to seawater. Samples designated TSA were prepared for electrochemical testing in the exact same way as for DSA, except for using Al5Mg alloy in the thermal spraying process. Samples designated CS were prepared from bare carbon steel plates that were cut to size and sealed off as required for attaining the desired surface area ratios of the various couples.
In the electrochemical experiments performed in fresh, circulated natural seawater, DSA samples were then coupled to CS samples in two different ratios; DSA:CS 100:1 (grey) and DSA:CS 10:1 (blue), simulating different defect sizes (see
Similarly, TSA samples were coupled to CS samples in two different ratios; TSA:CS 100:1 (grey) and TSA:CS 10:1 (blue). For use as reference, Anode samples directly cut from a cast Al-Zn-In-anode were coupled to CS in a ratio of Anode:CS 10:1 (red), see
The resulting protection current densities (mA/m2) plotted as a function of time (days) in
Thereby,
Although illustrated by way of example, a skilled person will realize that the technical effects and benefits of the cathodic protection system of the present invention is achievable within ranges, whereby modification of the invention within the language and wording of the claims is possible, and that any such modification, also if not literally meeting the claim language, is covered by the scope of protection as defined and afforded by the claims.
This written description uses examples to disclose the invention, including the preferred embodiments, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 20160374 | Mar 2016 | NO | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2017/054806 | 3/1/2017 | WO | 00 |
