EP0152336B1 - Verfahren zur Ausrichtung und zur Beschleunigung der Bildung von Ablagerungen in Meerwasser und Vorrichtung zur Durchfürung des Verfahrens - Google Patents

Verfahren zur Ausrichtung und zur Beschleunigung der Bildung von Ablagerungen in Meerwasser und Vorrichtung zur Durchfürung des Verfahrens Download PDF

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Publication number
EP0152336B1
EP0152336B1 EP85400167A EP85400167A EP0152336B1 EP 0152336 B1 EP0152336 B1 EP 0152336B1 EP 85400167 A EP85400167 A EP 85400167A EP 85400167 A EP85400167 A EP 85400167A EP 0152336 B1 EP0152336 B1 EP 0152336B1
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EP
European Patent Office
Prior art keywords
elements
cathode
anode
brucite
electrical connection
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP85400167A
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English (en)
French (fr)
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EP0152336A1 (de
Inventor
Antonius Olivier Streichenberger
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A Responsabilite Rep Marine Ltee Ste
Original Assignee
A Responsabilite Rep Marine Ltee Ste
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Application filed by A Responsabilite Rep Marine Ltee Ste filed Critical A Responsabilite Rep Marine Ltee Ste
Publication of EP0152336A1 publication Critical patent/EP0152336A1/de
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Publication of EP0152336B1 publication Critical patent/EP0152336B1/de
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Classifications

    • E—FIXED CONSTRUCTIONS
    • E02—HYDRAULIC ENGINEERING; FOUNDATIONS; SOIL SHIFTING
    • E02B—HYDRAULIC ENGINEERING
    • E02B17/00—Artificial islands mounted on piles or like supports, e.g. platforms on raisable legs or offshore constructions; Construction methods therefor
    • E02B17/0017—Means for protecting offshore constructions
    • E02B17/0026—Means for protecting offshore constructions against corrosion
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
    • E—FIXED CONSTRUCTIONS
    • E02—HYDRAULIC ENGINEERING; FOUNDATIONS; SOIL SHIFTING
    • E02B—HYDRAULIC ENGINEERING
    • E02B3/00—Engineering works in connection with control or use of streams, rivers, coasts, or other marine sites; Sealings or joints for engineering works in general
    • E02B3/04—Structures or apparatus for, or methods of, protecting banks, coasts, or harbours

Definitions

  • the present invention relates to the formation of calcareous concretions in the marine environment and more generally in an amphoteric electrolyte such as sea water, containing at least magnesium, calcium and carbonate ions.
  • cathodic protection methods by sacrificial anodes in which, to protect a metal surface, in general a ferrous metal, against corrosion of sea water, it is immersed in the water of sea or brings into contact with sea water in contact with the surface to be protected, a short distance from the latter, an anode electrode of a metal or a metal alloy having a spontaneous potential more electro-negative than the metal to be protected and for example in aluminum, zinc or magnesium alloys.
  • the ratio of the surface of the anode electrode to the surface to be protected is approximately 1/50 to 1 / 500th and the cathode current densities are of the order of 10- 3 A / m 2 to 0.5 A / m 2 so that the lifespan of the anodes is long, the protection being ensured during said lifespan.
  • brucite is produced in the form of large crystals with a porous structure and a low electrical resistivity while a low cathodic current density gives a deposit of small crystals with an impermeable structure and a high electrical resistivity.
  • the brucite with coarse crystallization dissolves in sea water while maintaining inside its mass a high pH corresponding to a pH of active deposition of aragonite. After removal of the anodic potential, the predominantly brucite deposit is transformed under certain conditions into a predominantly aragonite concretion.
  • the object of the present invention is to create, by the electrolytic deposition process known as sacrificial anodes, used in cathodic protection, a large layer of a predominantly large crystal brucite deposit giving a porous mass with a high water content capable of then transform into a concretion dominated by aragonite.
  • This object is achieved, in accordance with the invention, by using a metal cathode whose shape corresponds to the skeleton of the concretion to be obtained and an anode of a metal or metal alloy more electro-negative than the metal or the alloy of the cathode, by immersing the anode and the cathode in the marine environment containing magnesium, calcium and carbonate ions and by electrically interconnecting the two electrodes, the method according to the invention being characterized in.
  • the ratio of the surface of the anode to the surface of the cathode is between 1/30 and 2/1, with an anode mass sufficient to maintain this ratio inside the say limits during the period necessary for the deposition of the brucite-dominated concretion under the desired thickness.
  • the density of the cathode current is greater than 0.5 A / m 2 and generally 1 A / m 2 and the pH in contact with the cathode is greater than 9, 5, which results in a predominantly brucite deposit.
  • the period during which the anode, which gradually loses weight and surface area, continues to have a surface ratio greater than 1/30, depends on the resistivity and therefore in part on the salinity of the electrolyte which may be sea water, brackish water or water made artificially saline.
  • Brucite depending on the conditions of the deposit and in particular the speed, dissolves more or less quickly when the pH drops as a result of the reduction in the density of the cathode current.
  • the speed of dissolution of the brucite risks being so high that the slow growth of the aragonite crystals does not allow filling of the dissolution voids.
  • a cathodic current density ensuring a pH below the dissolution pH of the brucite but greater than the pH of the marine environment by means of a second sacrificed anode having a surface ratio at the surface of the cathode lower than that between 1/30 and 2/1, having ensured the deposition of the brucite-dominant concretion.
  • the spontaneous potential of steel in sea water at a temperature varying from 5 to 20 ° C, with a pH close to 8.20 and a salinity of 35% is between -800 and -1350 m V per relation to the reference electrode to the saturated calomel (DHW) according to the cathode current density applied.
  • the metal of the anode can be either an aluminum alloy with an electro-negative potential close to -1100 m V (ECS), a zinc alloy with an electro-negative potential close to -1050 m V (ECS) or a magnesium alloy with an electro-negative potential of around -1500 m V (DHW).
  • the cathode and the anode are in direct electrical contact, the elements forming the anode, for example bars or wires being inserted in a network of elements of corresponding shape forming the cathode with contacts distributed within the network.
  • the conditions imposed by the process mean that, in order to obtain the necessary cathodic current density, cathode elements whose cross section is greater than a minimum must be used. Consequently, in the network, the cathode elements have a significant spacing. However, it is often advantageous to increase the volume of the predominantly brucite deposit or its mechanical strength, which cannot be ensured by cathode elements with large spacing and, in accordance with the invention, this result is achieved by incorporating into the network forming the device, inert fillers, for example sand, natural or synthetic fibers. It also falls within the framework of the process of drowning at least the cathode in a porous mass of inert elements, for example sands or fibers, this mass being impregnated by the marine environment.
  • the present invention also relates to a device for implementing the method in order to form a concretion in the marine environment, this device comprising a structure of ferrous metal corresponding to the skeleton of the concretion to be formed, elements of a metal or alloy having a more electro-negative spontaneous potential than iron with an electrical connection between said structure and said elements, device characterized in that the electrical connection does not include a current source and the ratio of the surface of said elements to the surface of the structure being between 1/30 and 2/1.
  • the elements can be in the form of wires, bars, blades or bars or in the form of plates.
  • the electrical connection can be provided by an intermediate conductor electrically connected to the ferrous metal structure and to the element (s). It can also be direct, the elements being secured directly to the ferrous metal structure, for example by welding or mechanical tightening, so as to ensure said electrical connection.
  • the element When the element is in the form of a blade, or a plate of almost constant thickness, it preferably has an additional thickness forming a core whose peripheral surface is less than 1 / 30th of the surface surface of the structure, the electrical connection being provided on said core.
  • several types of elements are provided which have thicknesses perpendicular to their surface surfaces, which are variable, the total of the surface surfaces of the thickest elements being less than approximately one thirtieth of the surface surface of the structure. These last two characteristics are intended to leave after consumption of the thin part of the element which. ensures the predominant deposition of brucite, an anodic electro-negative element slowing down the dissolution of brucite and favoring the concretion of the mass of brucite by aragonite.
  • the ferrous metal structure is mechanically secured to electrically inert materials in a porous form such as sand enclosed in a porous envelope, natural or synthetic fibers, tubes or perforated sheaths , etc.
  • the ferrous metal structure having to have a low electrical resistance therefore a large section, section also necessary to allow the sinking in sandy bottoms, but a reduced surface in contact with the electrolyte to have a high density of cathode current, it is possible to sheath the structure with an insulator, reserving exposed areas according to rings, bands or braces for fixing the predominantly brucite deposit.
  • the anode element can be applied in the form of pads outside the sheath with direct electrical contact through the insulation.
  • the method and the device are capable of receiving numerous applications.
  • a first application is the accelerated construction of artificial underwater reefs, the skeleton of the reef being made of ferrous metal, for example in wires or iron bars with plates or bars of magnesium and / or aluminum fixed by being distributed in the structure.
  • a second application is the stabilization of the seabed such as the sandy bottom intended to receive constructions, this stabilization being able to be done either by sinking in the porous sandy mass, according to a network, of electrodes forming cathodes and anodes with the electrical interconnections or elongate element comprising both the cathode surfaces and the anode elements, either by forming a surface concretion in carpet by extending on the bottom a mesh or latticework welded in ferrous metal with associated anode elements.
  • a third application of great interest economical is the filling of cracks and clogging of joints in marine structures such as submerged or submerged dikes, various basins, etc. by inserting into the cracks or joints of an element in the form of a ribbon, a twist or the like comprising elements of ferrous metal and elements of aluminum, zinc or their alloys.

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  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Structural Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Civil Engineering (AREA)
  • Ocean & Marine Engineering (AREA)
  • Environmental & Geological Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Prevention Of Electric Corrosion (AREA)

Claims (15)

1. Verfahren zur Ausrichtung und Beschleunigung der Bildung von Ablagerungen in natürlichem oder künstlichem Meerwasser, bei dem man eine metallische Kathode, deren Form dem Skelett der zu erhaltenden Ablagerung entspricht, und eine Anode aus einem Metall oder einer metallischen Legierung, das bzw. die elektronegativer als das Metall oder die Legierung der Kathode ist, einsetzt, indem man die Anode und die Kathode in das Magnesium-, Kalzium- und Karbonationen enthaltende Meerwasser eintaucht und die beiden Elektroden elektrisch verbindet, dadurch gekennzeichnet, dass man keinen Strom zwischen den beiden Elektroden anlegt und dass das Verhältnis der Oberfläche der Anode zur Oberfläche der Kathode im Bereich von 1/30 bis 2/1 liegt, wobei die Masse der Anode ausreichend ist, um dieses Verhältnis im Inneren dieser Grenzen während der Zeitdauer zu halten, die zur Abscheidung der Ablagerung vorwiegend von Brucit unter der angestrebten Dicke erforderlich ist.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass man nach Bildung der vorwiegend aus Brucit bestehenden Abscheideschicht gewünschter Dicke eine Kathodische Stromdichte, die einen pH-Wert unter dem Brucitauflösungs-pH-Wert, jedoch über dem pH-Wert des Meerwassers sichert, mittels einer zweiten Opferanode aufrechterhält, die ein niedrigeres Oberflächenverhältnis zur Oberfläche der Kathode als das im Bereich von 1/30 bis 2/1 liegende derjenigen aufweist, die die Abscheidung der Ablagerung vorwiegend von Brucit sicherte.
3. Verfahren nach irgendeinem der Ansprüche 1 und 2, dadurch gekennzeichnet, dass man als Metall der Anode Aluminium, Zink, Magnesium oder ihre Legierungen verwendet.
4. Verfahren nach irgendeinem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Kathode und die Anode in direktem elektrischen Kontakt sind, wobei die die Anode bildenden Elemente, z.B. Stangen oder Drähte, in ein Netz von die Kathode bildenden Elementen entsprechender Form mit im Inneren des Netzes verteilten Kontakten eingefügt sind.
5. Verfahren nach irgendeinem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass man in das die Vorrichtung bildende Netz inerte Beschickungen, z.B. Sande, natürliche oder künstliche Fasern, einbringt.
6. Verfahren nach irgendeinem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass man wenigstens die Kathode in einer porösen Masse inerter Elemente, z.B. Sande oder Fasern, einbettet, welche Masse durch das Meerwasser imprägniert wird.
7. Vorrichtung zur Durchführung des Verfahrens nach Anspruch 1, mit einem dem Skelett der zu bildenden Ablagerung entsprechenden Aufbau aus einem Eisenmetall und Elementen aus einem Metall oder einer Legierung mit einem selbständigen elektronegativeren Potential als das Eisen mit einer elektrischen Verbindung zwischen dem Aufbau und den Elementen, dadurch gekennzeichnet, dass die elektrische Verbindung keine Stromquelle aufweist und dass das Verhältnis der Oberfläche der Elemente zur Oberfläche des Aufbaus im Bereich von 1/30 bis 2/1 liegt.
8. Vorrichtung nach Anspruch 7, dadurch gekennzeichnet, dass die Elemente in Form von Drähten, Stangen, Blättern oder Stäben oder in Form von Plättchen sind.
9. Vorrichtung nach irgendeinem der Ansprüche 7 und 8, dadurch gekennzeichnet, dass die elektrische Verbindung durch einen Zwischenleiter gesichert wird, der elektrisch mit dem Aufbau aus Eisenmetall und dem oder den Elementen verbunden ist.
10. Vorrichtung nach irgendeinem der Ansprüche 7 und 8, dadurch gekennzeichnet, dass die elektrische Verbindung direkt ist, wobei die Elemente mit dem Aufbau aus Eisenmetall direkt, z. B. durch Schweissen oder mechanisches Klemmen, derart fest verbunden sind, um die elektrische Verbindung zu sichern.
11. Vorrichtung nach irgendeinem der Ansprüche 7 bis 10, dadurch gekennzeichnet, dass das Element in Form eines Blattes oder eines Plättchens etwa konstanter Dicke ist und eine Überdicke unter Bildung eines Ansatzkerns aufweist, dessen Umfangsoberfläche unter 1/30 der Oberfläche des Aufbaus ist, wobei die elektrische Verbindung auf diesem Ansatzkern gesichert wird.
12. Vorrichtung nach irgendeinem der Ansprüche 7 bis 10, dadurch gekennzeichnet, dass mehrere Arten von Elementen vorgesehen sind, die variable, zu ihren Oberflächen senkrechte Dicken aufweisen, wobei die Gesamtheit der Oberflächen der dicksten Elemente unter etwa dem Dreissigstel der Oberfläche des Aufbaus ist.
13. Vorrichtung nach irgendeinem der Ansprüche 7 bis 12, dadurch gekennzeichnet, dass der Aufbau aus Eisenmetall mechanisch mit elektrisch inerten Materialien verbunden ist, die sich in poröser Form befinden.
14. Vorrichtung nach Anspruch 13, dadurch gekennzeichnet, dass der Aufbau mit einem Isolierstoff ummantelt ist, wobei blanke Zonen längs Ringen, Bändern oder Kreuzformen belassen sind.
15. Vorrichtung nach Anspruch 14, dadurch gekennzeichnet, dass das anodische Element in Form von Streifen an der Aussenseite der Ummantelung mit direktem elektrischem Kontakt zwischen dem Aufbau und dem Element durch die Ummantelung hindurch angebracht ist.
EP85400167A 1984-02-03 1985-02-01 Verfahren zur Ausrichtung und zur Beschleunigung der Bildung von Ablagerungen in Meerwasser und Vorrichtung zur Durchfürung des Verfahrens Expired EP0152336B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8401697A FR2559178B1 (fr) 1984-02-03 1984-02-03 Procede pour orienter et accelerer la formation de concretions en milieu marin et dispositif pour sa mise en oeuvre
FR8401697 1984-02-03

Publications (2)

Publication Number Publication Date
EP0152336A1 EP0152336A1 (de) 1985-08-21
EP0152336B1 true EP0152336B1 (de) 1988-04-20

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EP85400167A Expired EP0152336B1 (de) 1984-02-03 1985-02-01 Verfahren zur Ausrichtung und zur Beschleunigung der Bildung von Ablagerungen in Meerwasser und Vorrichtung zur Durchfürung des Verfahrens

Country Status (5)

Country Link
US (1) US4623433A (de)
EP (1) EP0152336B1 (de)
CA (1) CA1249977A (de)
DE (1) DE3562279D1 (de)
FR (1) FR2559178B1 (de)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3930741C1 (de) * 1989-09-14 1990-12-13 Lemfoerder Metallwaren Ag, 2844 Lemfoerde, De
FR2762861B1 (fr) * 1997-04-30 1999-07-16 Ifremer Procede de formation d'un beton naturellement arme dans un milieu electrolytique et cathode tridimensionnelle
AU2065599A (en) * 1998-01-13 1999-08-02 Anthony Maxwell Marine stock enhancement process
FR2862057B1 (fr) * 2003-11-07 2008-02-15 Bernard Vedrenne Procede de regulation de la formation du geo-ciment/ geo-beton naturel
WO2008103675A1 (en) * 2007-02-20 2008-08-28 Brandon Nichols Apparatus, system and method of sea water fertilization
WO2013148279A1 (en) * 2012-03-29 2013-10-03 Calera Corporation Methods and systems for utilizing carbide lime
RU2558442C1 (ru) * 2013-11-19 2015-08-10 Общество с ограниченной ответственностью "Газпром добыча шельф Южно-Сахалинск" (ООО "Газпром добыча шельф Южно-Сахалинск") Способ консолидации грунтового основания гидротехнического сооружения
US9902652B2 (en) 2014-04-23 2018-02-27 Calera Corporation Methods and systems for utilizing carbide lime or slag
FR3093735B1 (fr) 2019-03-15 2023-05-19 Geocorail Dispositif pour former des concretions a source autonome regulee
WO2021173790A1 (en) 2020-02-25 2021-09-02 Arelac, Inc. Methods and systems for treatment of lime to form vaterite
CN116018195A (zh) 2020-06-30 2023-04-25 艾瑞莱克公司 使用电窑从煅烧的石灰石形成球霰石的方法和系统

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Publication number Priority date Publication date Assignee Title
GB540487A (en) * 1940-03-27 1941-10-20 George Chandler Cox Improvements relating to the protection of metallic surfaces in contact with sea water and similar liquids
FR1321837A (fr) * 1962-05-08 1963-03-22 Thomson Houston Comp Francaise Procédé pour revêtir des alliages de fer
US4246075A (en) * 1979-03-19 1981-01-20 Marine Resources Company Mineral accretion of large surface structures, building components and elements
AU566350B2 (en) * 1982-10-29 1987-10-15 British Petroleum Company Plc, The Stabilisation of particulate material
CA1201608A (en) * 1982-11-22 1986-03-11 Yoshiteru Sonoda Precision pressure gauge

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Publication number Publication date
DE3562279D1 (en) 1988-05-26
EP0152336A1 (de) 1985-08-21
FR2559178A1 (fr) 1985-08-09
US4623433A (en) 1986-11-18
CA1249977A (fr) 1989-02-14
FR2559178B1 (fr) 1986-05-30

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