CN111534822A - Deep sea equipment cathode protection device based on biological anode - Google Patents
Deep sea equipment cathode protection device based on biological anode Download PDFInfo
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- CN111534822A CN111534822A CN202010392077.3A CN202010392077A CN111534822A CN 111534822 A CN111534822 A CN 111534822A CN 202010392077 A CN202010392077 A CN 202010392077A CN 111534822 A CN111534822 A CN 111534822A
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- deep sea
- bioanode
- sea equipment
- potentiometer
- protective cover
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F13/00—Inhibiting corrosion of metals by anodic or cathodic protection
- C23F13/02—Inhibiting corrosion of metals by anodic or cathodic protection cathodic; Selection of conditions, parameters or procedures for cathodic protection, e.g. of electrical conditions
- C23F13/06—Constructional parts, or assemblies of cathodic-protection apparatus
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F2213/00—Aspects of inhibiting corrosion of metals by anodic or cathodic protection
- C23F2213/30—Anodic or cathodic protection specially adapted for a specific object
- C23F2213/31—Immersed structures, e.g. submarine structures
Abstract
The invention discloses a deep sea equipment cathode protection device based on a biological anode, which relates to the field of deep sea metal corrosion prevention, and comprises deep sea equipment, a bottom support and at least one biological anode, wherein the bottom support is arranged at the bottom of the deep sea equipment, and the biological anode is arranged at the bottom of the bottom support; the biological anode comprises a protective cover, a plurality of carbon brushes and electrogenesis bacteria, the carbon brushes and the electrogenesis bacteria are arranged in the protective cover, the electrogenesis bacteria are attached to the carbon brushes and connected through a conducting wire, the side wall of the protective cover is a side wall with a gap, the bottom of the protective cover is closed, the top of the protective cover is opened, the bottom of the biological anode is connected with deep sea equipment through a bottom-sitting support, the top of the biological anode is inserted into submarine sediments, the electrogenesis bacteria react with the submarine sediments, cathode current protection is provided for the deep sea equipment, the cathode protection device does not need to be replaced regularly, energy does not need to be provided additionally, and the.
Description
Technical Field
The invention relates to the field of deep sea metal corrosion prevention, in particular to a deep sea equipment cathode protection device based on a biological anode.
Background
Deep sea metal structures require cathodic protection measures to prevent or mitigate metal corrosion, and current cathodic protection methods mainly include sacrificial anodic methods and forced current methods. The sacrificial anode method adopts metals or alloys with lower potential sequence such as Mg, Zn, Al and the like in seawater to prepare the sacrificial anode, and provides cathodic protection current for the deep sea metal device through the oxidation of the sacrificial anode in the seawater. The disadvantage of this method is that the sacrificial anode is continuously consumed during use, has a limited service life and must be replaced periodically. For the sacrificial anode used in the deep sea environment, the replacement operation cost is high and the difficulty is high.
The forced current law is to control the potential or current density of the deep sea structure by a potentiostat or a constant current source, etc. to polarize the cathode of the protected metal, thereby achieving the purpose of corrosion prevention. However, this method requires the use of an external power source, not only causing additional energy consumption, but also potentially causing electromagnetic interference with nearby metal structures. Meanwhile, the intensity of the forced current also needs to be accurately controlled, and once the forced current is too large, the hydrogen evolution risk exists, and the damage is caused to metals such as titanium alloy and the like.
Disclosure of Invention
The invention provides a cathode protection device for deep sea equipment based on a biological anode, aiming at the problems and technical requirements, wherein the biological anode containing electrogenesis bacteria is utilized to directly oxidize seabed sediments so as to provide cathode current protection for the deep sea equipment.
The technical scheme of the invention is as follows:
a cathodic protection device of deep sea equipment based on a biological anode comprises the deep sea equipment, a bottom support and at least one biological anode, wherein the bottom support is arranged at the bottom of the deep sea equipment, and the biological anode is arranged at the bottom of the bottom support;
the bioanode comprises a protective cover, a plurality of carbon brushes and electrogenic bacteria, the carbon brushes and the electrogenic bacteria are arranged in the protective cover, the electrogenic bacteria are attached to the carbon brushes, the carbon brushes are connected through a conducting wire, the side wall of the protective cover is a side wall with a gap, the bottom of the protective cover is closed, the top of the protective cover is opened, the bottom of the bioanode is connected with deep sea equipment through a bottom-sitting support, the top of the bioanode is inserted into submarine sediments, and the electrogenic bacteria react with the submarine sediments to provide cathodic current protection for the deep sea.
The further technical scheme is that when the deep sea equipment lands on the sea bottom, the seabed sediments enter the protective cover from the top of the biological anode, the electrogenic bacteria are oxidized and decomposed to generate new electrogenic bacteria, and meanwhile, the old deep sea sediments are discharged from the gap of the side wall of the protective cover, which is not inserted into the seabed sediments, so that the deep sea sediments in the protective cover are updated.
The further technical scheme is that when the deep sea equipment leaves the seabed and continues to sail, seabed sediments entering the protective cover are retained in the protective cover under the action of the carbon brush to continuously provide reaction substrates for electrogenic bacteria, and the bioanode continuously provides cathodic current protection for the deep sea equipment.
The further technical proposal is that the biological anode is obtained through a pre-inoculation stage, and the pre-inoculation stage comprises the following steps: the method comprises the steps of assembling an inoculation reactor, wherein the inoculation reactor comprises an anode chamber and a cathode chamber, the anode chamber and the cathode chamber are isolated through a proton exchange membrane, activated sludge containing electrogenic bacteria is inoculated on a carbon brush of a biological anode arranged in the anode chamber, seabed sediment is injected into the anode chamber to serve as a reaction substrate, a cathode solution is injected into the cathode chamber to serve as a cathode electron acceptor, the biological anode and the cathode chamber are connected through an external circuit to form a loop, mature electrogenic bacteria are finally formed on the carbon brush after culturing for a preset time, and the mature electrogenic bacteria are attached to the carbon brush in the form of a biological membrane.
The bottom of the biological anode is connected with a bottom support through a detection and debugging device, the detection and debugging device comprises an adjustable resistor, a first potentiometer and a first reference electrode, one end of the adjustable resistor is connected with the bottom support, the other end of the adjustable resistor is respectively connected with each biological anode, the adjustable resistor is used for adjusting the polarization current intensity between the biological anode and deep sea equipment, one end of the first potentiometer is connected with the first reference electrode, the other end of the first potentiometer is connected with the adjustable resistor and the common end of the biological anode, the first reference electrode is also inserted into the seabed sediment, and the first potentiometer and the first reference electrode are used for monitoring the current protection state of the biological anode;
one end of the second potentiometer is connected with the second reference electrode, the other end of the second potentiometer is connected with the deep sea equipment, and the second potentiometer and the second reference electrode are used for monitoring the current protection state of the deep sea equipment.
The further technical scheme is that the bottom support is a metal bottom support, the adjustable resistor and the first potentiometer are arranged on the metal bottom support, and the minimum resistance formed by the metal bottom support and a lead for connecting the biological anode and the deep sea equipment is no more than 10 omega at most.
The beneficial technical effects of the invention are as follows:
because the organic matter content in the submarine sediment is rich and the diffusion transmission flow exists in the submarine sediment, when the deep-sea equipment lands on the seabed, the bottom-sitting support not only can support the deep-sea equipment to avoid the deep-sea equipment from directly contacting with the seabed, but also can utilize the falling action to enable the open top of the bioanode to be inserted into the submarine sediment, the electrogenic bacteria on the carbon brush can continuously utilize the degradable organic matter in the submarine sediment to continuously provide cathode protection current for the deep-sea equipment, meanwhile, the old deep-sea sediment is discharged from the gap of the side wall of the protective cover which is not inserted into the submarine sediment, the updating of the deep-sea sediment is realized, the polarization current intensity between the bioanode and the deep-sea equipment is adjusted through the adjustable resistor, the current protection states of the bioanode and the deep-sea equipment are jointly monitored through the potentiometer and the reference electrode, and compared with the, and no additional energy supply is required, so the cathodic protection device has a remarkable advantage of providing cathodic protection for deep-sea stationary metal devices.
Drawings
Fig. 1 is a schematic structural diagram of a bioanode-based deep-sea equipment cathodic protection device provided by the application.
Fig. 2 is a schematic diagram of the potential of the bioanode and the deep sea equipment provided by the present application as a function of polarization current density.
FIG. 3 is a schematic illustration of an inoculation reactor as provided herein.
Detailed Description
The following further describes the embodiments of the present invention with reference to the drawings.
The application discloses cathodic protection device is equipped in deep sea based on biological anode, its schematic structure is shown in figure 1, and cathodic protection device includes that deep sea is equipped 1, sits bottom bracket 2 and at least one biological anode 3, sits bottom bracket 2 and sets up in the bottom that deep sea was equipped 1, and biological anode 3 sets up in the bottom of sitting bottom bracket 2. Wherein the number of the bioanode 3 may be set one or more bioanodes 3 to adjust the maximum cathodic protection current according to the required cathodic protection current intensity of the protected deep sea equipment 1. Optionally, the deep sea equipment 1 is titanium alloy metal equipment. The submersible support 2 not only supports the deep sea equipment 1 from direct contact with the seabed, but also allows the open top of the bioanode 3 to be inserted into the seabed sediment 4 by a lowering action.
The bioanode 3 comprises a protective cover 301, a plurality of carbon brushes 302 and electrogenic bacteria 303, wherein the carbon brushes 302 and the electrogenic bacteria 303 are arranged in the protective cover 301, the electrogenic bacteria 303 are attached to the carbon brushes 302, the carbon brushes 302 are connected through a conducting wire, the side wall of the protective cover 301 is a side wall with a gap, the bottom of the protective cover 301 is closed, the top of the protective cover is opened, the bottom of the bioanode 3 is connected with the deep sea equipment 1 through a bottom-seated support 2, the top of the bioanode 3 is inserted into the seabed sediments 4, and the electrogenic bacteria 303 react with the seabed sediments 4 to provide cathodic current.
Optionally, the bottom of the bioanode 3 is connected to the subrack 2 through a detection and debugging device, the detection and debugging device includes an adjustable resistor 5, a first potentiometer 6 and a first reference electrode 7, one end of the adjustable resistor 5 is connected to the subrack 2, the other end of the adjustable resistor is connected to each bioanode 3, the adjustable resistor 5 is used for adjusting the polarization current intensity between the bioanode 3 and the deep sea equipment 1, one end of the first potentiometer 6 is connected to the first reference electrode 7, the other end of the first potentiometer is connected to the common end of the adjustable resistor 5 and the bioanode 3, the first reference electrode 7 is also inserted into the submarine sediment 4, and the first potentiometer 6 and the first reference electrode 7 are used for monitoring the current protection state of the bioanode 3.
One end of the second potentiometer 8 is connected with the second reference electrode 9, the other end of the second potentiometer is connected with the deep sea equipment 1, and the second potentiometer 8 and the second reference electrode 9 are used for monitoring the current protection state of the deep sea equipment 1.
A schematic diagram of the potential variation of the bioanode 3 and the protected deep sea equipment 1 along with the polarization current density is shown in FIG. 2, and it can be seen that the bioanode 3 has stable potential under different polarization current densities, and can provide stable cathodic protection current for the protected deep sea equipment 1.
Optionally, the bottom-supporting frame 2 is a metal bottom-supporting frame, the adjustable resistor 5 and the first potentiometer 6 are arranged on the metal bottom-supporting frame, and the minimum resistance formed by the metal bottom-supporting frame and a wire for connecting the bioanode 3 with the deep-sea equipment 1 is no more than 10 Ω at most, so that the bioanode 3 can be reliably connected with the protected deep-sea equipment 1.
In the present application, the bioanode 3 is obtained by a pre-inoculation stage, as shown in fig. 3, comprising: assembling an inoculation reactor, wherein the inoculation reactor comprises an anode chamber and a cathode chamber, the anode chamber and the cathode chamber are separated by a proton exchange membrane, inoculating activated sludge containing electrogenic bacteria on a carbon brush 302 of a biological anode 3 arranged in the anode chamber, injecting seabed sediment 4 into the anode chamber as a reaction substrate, and injecting a cathode solution 10 into the cathode chamber as a cathode electron acceptor, wherein the cathode solution is a 50mM potassium ferricyanide solution. The biological anode 3 and the cathode chamber are connected through an external circuit to form a loop, optionally, the external circuit comprises a 50 Ω load R, a third potentiometer 11 and a third reference electrode 12, one end of the third potentiometer 11 is connected with the biological anode 3, the other end of the third potentiometer is respectively connected with one end of the 50 Ω load R and the third reference electrode 12, the other end of the 50 Ω load R is connected with the cathode solution 10, and the third reference electrode 12 is placed in the seafloor sediment 4. After culturing for a predetermined time, the potential of the anode chamber is reduced to below-0.5V (vs Ag/AgCl reference electrode), mature electrogenic bacteria are finally formed on the carbon brush 302, and the mature electrogenic bacteria are attached to the carbon brush 302 in the form of a biological membrane, thereby completing the pre-inoculation stage.
Alternatively, first reference electrode 7, second reference electrode 9, and third reference electrode 12 all use Ag/AgCl reference electrodes.
When the deep sea equipment 1 is landed on the seabed, as shown by the arrow direction in fig. 1, the seabed sediment 4 enters the protective cover 301 from the top of the bioanode 3, the electricity generating bacteria 303 oxidatively decomposes the seabed sediment 4 to generate new electricity generating bacteria, and simultaneously, the old deep sea sediment is discharged from the gap of the side wall of the protective cover where the seabed sediment 4 is not inserted, so that the deep sea sediment 4 in the protective cover 301 is renewed.
When the deep sea equipment 1 leaves the seabed to continue navigation, seabed sediments 4 entering the protective cover 301 are retained in the protective cover 301 under the action of the carbon brushes 302 to continuously provide reaction substrates for the electrogenic bacteria 303, and the bioanode 3 is continuously provided with cathodic current protection for the deep sea equipment 1.
The principle of the cathodic protection device of the application is as follows:
the seabed sediment 4 is formed by remains of animals and plants, silt and the like through long-time sedimentation and contains rich organic matters. The electricity generating bacteria 303 are a kind of bacteria which can oxidize and decompose degradable organic matters in the seabed sediment 4 in the self metabolic process and simultaneously provide electrons for a high potential electron acceptor continuously, and widely exist in the marine environment. The biological anode 3, namely, the electric conductor attached with the electrogenic bacteria 303 is used as the anode in the electrochemical system, and the deep sea equipment 1 to be protected in the sea water is used as the cathode. Under the catalytic action of the electricity generating bacteria 303, the biological anode 3 can decompose a plurality of organic matters such as acetic acid, propionic acid, butyric acid, lactic acid and the like in the seabed sediment 4, and part of the organic matters which cannot be directly utilized by the electricity generating bacteria 303 can also be decomposed into secondary products which can be utilized by the electricity generating bacteria 303 under the action of other microbial colonies in the seabed sediment 4. The bioanode 3 generates electrons and conducts and collects the electrons through the carbon brush 302, and provides cathodic current protection for the deep sea equipment 1 by taking the deep sea equipment 1 as a cathode so as to form stable cathodic current, compared with the traditional cathodic protection method, the method does not need to be replaced regularly, and does not need to provide extra energy, so that the cathodic protection device has a remarkable advantage in providing cathodic protection for deep sea fixed metal devices.
Typical electrode reactions of a bioanode may include, but are not limited to, the following electrode reactions:
C2H4O2+2H2O→2CO2+8H++8e-
C3H6O2+4H2O→3CO2+14H++14e-
C4H8O2+2H2O→2C2H4O2+4H++4e-
3C4H8O2+2H2O→4C3H6O2+4H++4e-
what has been described above is only a preferred embodiment of the present application, and the present invention is not limited to the above embodiment. It is to be understood that other modifications and variations directly derivable or suggested by those skilled in the art without departing from the spirit and concept of the present invention are to be considered as included within the scope of the present invention.
Claims (6)
1. The cathodic protection device for the deep sea equipment based on the biological anode is characterized by comprising the deep sea equipment, a bottom support and at least one biological anode, wherein the bottom support is arranged at the bottom of the deep sea equipment, and the biological anode is arranged at the bottom of the bottom support;
the bioanode includes the safety cover and arranges in a plurality of carbon brush and electrogenesis bacterium in the safety cover, electrogenesis bacterium is attached to on the carbon brush, each the carbon brush passes through the wire and links to each other, the lateral wall of safety cover is for taking the lateral wall in space, bottom closed, open-top, bioanode's bottom is passed through sit the end leg joint the deep sea is equipped, the top of bioanode is inserted in the submarine sediment, electrogenesis bacterium with the submarine sediment reacts, for the deep sea is equipped and is provided cathodic current protection.
2. The cathodic protection device as set forth in claim 1 wherein when the deep sea equipment is landed on the seabed, the seabed sediments enter the protective cover from the top of the bioanode, the electrogenic bacteria oxidatively decompose the seabed sediments to generate new electrogenic bacteria, and old deep sea sediments are discharged from the gap of the side wall of the protective cover where the seabed sediments are not inserted, thereby realizing the renewal of the deep sea sediments in the protective cover.
3. The cathodic protection device as recited in claim 1 wherein, when the deep sea equipment is further sailed away from the sea floor, seabed sediment entering the protective cover is retained in the protective cover by the carbon brushes and continuously provides reaction substrates for the electrogenic bacteria, thereby realizing that the bioanode continuously provides cathodic current protection for the deep sea equipment.
4. A cathodic protection device as claimed in any one of claims 1 to 3, wherein the bioanode is obtained by a pre-seeding stage comprising: assembling an inoculation reactor, wherein the inoculation reactor comprises an anode chamber and a cathode chamber, the anode chamber and the cathode chamber are separated by a proton exchange membrane, inoculating activated sludge containing the electrogenic bacteria on a carbon brush of the bioanode arranged in the anode chamber, injecting the seabed sediment into the anode chamber as a reaction substrate, injecting a cathode solution into the cathode chamber as a cathode electron acceptor, connecting the bioanode and the cathode chamber through an external circuit to form a loop, and finally forming mature electrogenic bacteria on the carbon brush after culturing for a preset time, wherein the mature electrogenic bacteria are attached to the carbon brush in the form of a biological membrane.
5. The cathodic protection device according to claim 1, wherein the bottom of the bioanode is connected to the bottom bracket through a detection and adjustment device, the detection and adjustment device comprises an adjustable resistor, a first potentiometer and a first reference electrode, one end of the adjustable resistor is connected to the bottom bracket, the other end of the adjustable resistor is connected to each bioanode, the adjustable resistor is used for adjusting the polarization current intensity between the bioanode and the deep sea equipment, one end of the first potentiometer is connected to the first reference electrode, the other end of the first potentiometer is connected to the common end of the adjustable resistor and the bioanode, the first reference electrode is also inserted into the seafloor sediment, and the first potentiometer and the first reference electrode are used for monitoring the current protection state of the bioanode;
one end of the second potentiometer is connected with the second reference electrode, the other end of the second potentiometer is connected with the deep sea equipment, and the second potentiometer and the second reference electrode are used for monitoring the current protection state of the deep sea equipment.
6. The cathodic protection device according to claim 5, wherein the submersible support is a metal submersible support, the adjustable resistor and the first potentiometer are arranged on the metal submersible support, and the minimum resistance of the metal submersible support and the wire connecting the bioanode and the deep sea equipment is not more than 10 Ω at most.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010392077.3A CN111534822B (en) | 2020-05-11 | 2020-05-11 | Deep sea equipment cathode protection device based on biological anode |
| PCT/CN2021/089504 WO2021227839A1 (en) | 2020-05-11 | 2021-04-25 | Bioanode-based cathodic protection device for deep-sea equipment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010392077.3A CN111534822B (en) | 2020-05-11 | 2020-05-11 | Deep sea equipment cathode protection device based on biological anode |
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| CN111534822A true CN111534822A (en) | 2020-08-14 |
| CN111534822B CN111534822B (en) | 2022-04-26 |
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| CN (1) | CN111534822B (en) |
| WO (1) | WO2021227839A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2021227839A1 (en) * | 2020-05-11 | 2021-11-18 | 中国船舶科学研究中心 | Bioanode-based cathodic protection device for deep-sea equipment |
| FR3123662A1 (en) * | 2021-06-08 | 2022-12-09 | Corrohm | Device for cathodic protection of a metal structure against corrosion |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN111534822B (en) | 2022-04-26 |
| WO2021227839A1 (en) | 2021-11-18 |
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