CN109415838B - Electrolytic degreasing method and electrolytic degreasing device - Google Patents

Electrolytic degreasing method and electrolytic degreasing device Download PDF

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CN109415838B
CN109415838B CN201780036041.8A CN201780036041A CN109415838B CN 109415838 B CN109415838 B CN 109415838B CN 201780036041 A CN201780036041 A CN 201780036041A CN 109415838 B CN109415838 B CN 109415838B
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cleaned
electrolytic
alkaline
degreasing
electrolytic degreasing
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CN109415838A (en
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小川健二
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Fudauchi Kogyo Co ltd
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Fudauchi Kogyo Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
    • B08B3/04—Cleaning involving contact with liquid
    • B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
    • B08B3/04—Cleaning involving contact with liquid
    • B08B3/10—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
    • B08B3/04—Cleaning involving contact with liquid
    • B08B3/10—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration
    • B08B3/12—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration by sonic or ultrasonic vibrations
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
    • C02F1/36—Treatment of water, waste water, or sewage with mechanical oscillations ultrasonic vibrations
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/19—Iron or steel
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G3/00—Apparatus for cleaning or pickling metallic material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F7/00—Constructional parts, or assemblies thereof, of cells for electrolytic removal of material from objects; Servicing or operating

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Electrochemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Cleaning By Liquid Or Steam (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Physical Water Treatments (AREA)

Abstract

The invention provides an electrolytic degreasing method and an electrolytic degreasing device using the same, wherein the electrolytic degreasing method can remove pollutants such as oil from the surface of an object to be cleaned more reliably and prevent the removed pollutants from adhering to the object to be cleaned again. The electrolytic degreasing method of the present invention is a method for removing contaminants such as oil adhered to the surface of an object to be cleaned with alkaline electrolytic water, characterized in that the object to be cleaned and an anode electrode are arranged in the alkaline electrolytic water and energized to cathodically polarize the object to be cleaned, thereby forming hydrogen bubbles having a diameter of 20nm to 10 [ mu ] m on the surface of the object to be cleaned, the hydrogen bubbles are broken in the vicinity of the surface of the object to be cleaned, and the contaminants adhered to the surface of the object to be cleaned are removed by a shock wave generated by the breaking, wherein the anode electrode has an electrode catalyst layer containing 10g/m on the surface thereof2～20g/m2Iridium oxide in an amount. The electrolytic degreasing device of the invention is used for implementing the method.

Description

Electrolytic degreasing method and electrolytic degreasing device
Technical Field
The present invention relates to an electrolytic degreasing method for removing contaminants adhering to the surface of an object to be cleaned, and an electrolytic degreasing apparatus for performing the electrolytic degreasing method.
Background
In general, when a plating treatment or a coating treatment is performed on the surface of an industrial part, it is necessary to remove contaminants present on the surface to be treated and perform a treatment for removing contaminants present on the surface of the industrial part as a pretreatment before the plating treatment or the coating treatment is performed. The contaminants are oil components such as water-soluble oil and nonaqueous oil used in the production process in many cases. After these contaminants remain on the surface of the industrial member, the plated or coated film itself cannot be formed, or even if the plated or coated film can be formed, the film thickness thereof greatly fluctuates.
Therefore, degreasing treatment has been conventionally used as a pretreatment before plating or coating treatment is performed on the surface of an industrial member. As a degreasing method, there are alkaline degreasing, electrolytic degreasing, and the like. Alkaline degreasing is performed by immersing a material to be treated in an alkaline degreasing solution mainly containing various alkaline compounds such as hydroxide, phosphate, silicate, and carbonate and a surfactant. In the same manner as the alkaline degreasing, the object to be treated is electrolyzed using an alkaline degreasing solution, and the dirt is physically removed by the gas generated on the surface. When the object to be treated is a cathode, the scale on the surface is physically removed by hydrogen gas generated on the surface, and when the object to be treated is an anode, the scale on the surface is oxidized and decomposed by oxygen gas generated on the surface, and the scale is removed.
For example, patent document 1 is a prior art using an electrolytic degreasing method. Patent document 1 discloses a "method for electrolytically degreasing an electrically conductive member, which includes a step of immersing an electrically conductive member having a surface with foreign matter such as oil, rust, or dirt as a cathode and a metal electrode as an anode in an electrolytic solution, a step of applying a voltage between the anode and the cathode in the electrolytic solution to cause a current to flow between the two electrodes, thereby continuously generating bubbles on the surface of the electrically conductive member, and a step of removing the foreign matter from the surface of the electrically conductive member by mechanical agitation caused by the bubbles".
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 10-245700
Disclosure of Invention
Problems to be solved by the invention
However, the technique of patent document 1 is to electrolyze an electrolytic solution as an alkaline degreasing solution and remove foreign matter on the surface of a conductive member by mechanical agitation and cathode reduction due to hydrogen gas generated on the surface of the conductive member constituting a cathode, and thus cannot remove foreign matter on a conductive member having a complicated fine unevenness on the surface. This is because, when an electrolytic solution containing an alkaline compound and a surfactant is electrolyzed, hydrogen bubbles generated on the surface of the conductive member are large, and when a concave portion smaller than the hydrogen bubbles is present on the surface of the conductive member, the hydrogen bubbles cannot enter the concave portion.
Further, in patent document 1, since foreign matter such as oil removed from the surface of the conductive member by electrolytic degreasing floats in the electrolyte, when the conductive member is lifted up from the electrolyte, the foreign matter separated from the surface thereof adheres again, and there is a problem that the foreign matter is taken into a tank in which the next step is performed. Further, there is a problem that the treatment of wastewater becomes complicated with an electrolyte having a high concentration of oil or the like.
In view of the above problems, there is a demand for the development of an electrolytic degreasing method and an electrolytic degreasing apparatus, which can remove contaminants such as oil more reliably even if an object to be cleaned has complicated fine irregularities on its surface and can solve the problem that the removed contaminants are attached again to the object to be cleaned.
Means for solving the problems
The present inventors have made intensive studies to solve the above problems, and as a result, have conceived an electrolytic degreasing method and an electrolytic degreasing apparatus as described below.
The electrolytic degreasing method comprises the following steps: the electrolytic degreasing method of the present invention uses alkaline electrolyzed water for removalA method for removing contaminants such as oil adhered to the surface of an object to be cleaned, characterized in that the object to be cleaned and an anode electrode having an electrode catalyst layer containing 10g/m of an electrolyte are arranged in alkaline electrolytic water and energized to cathodically polarize the object to be cleaned, thereby forming hydrogen bubbles having a diameter of 20nm to 10 [ mu ] m on the surface of the object to be cleaned, the hydrogen bubbles are broken in the vicinity of the surface of the object to be cleaned, and the contaminants adhered to the surface of the object to be cleaned are removed by shock waves (cavitation) generated by the breaking, wherein the anode electrode has an electrode catalyst layer containing 10g/m of an electrolyte2～20g/m2Iridium oxide in an amount.
In the electrolytic degreasing method of the present invention, the alkaline electrolytic water is preferably an aqueous solution containing potassium carbonate and potassium hydroxide and having a pH of 11 to 13.
In the electrolytic degreasing method of the present invention, it is preferable that the hydrogen bubbles are irradiated with ultrasonic waves in alkaline electrolytic water to break the hydrogen bubbles in the vicinity of the surface of the object to be cleaned.
In the electrolytic degreasing method of the present invention, it is preferable that the superoxide anion generated at the anode electrode when the current is applied and the oil component removed from the surface of the object to be cleaned are reacted in the alkaline electrolytic water to decompose the oil component into carbon and carbon dioxide.
An electrolytic degreasing device: the electrolytic degreasing apparatus of the present invention is an electrolytic degreasing apparatus for cleaning a surface of an object to be cleaned by the above-mentioned electrolytic degreasing method, and is characterized by comprising
A degreasing tank for storing alkaline electrolyzed water,
an anode electrode disposed in the degreasing tank,
an energizing means for forming hydrogen bubbles having a diameter of 20nm to 10 μm on the surface of the object to be cleaned by placing the object to be cleaned in the alkaline electrolytic water in a state of being immersed and cathodically polarizing the object to be cleaned,
a hydrogen bubble breaking means for breaking the hydrogen bubbles near the surface of the object to be cleaned, and
the circulation filtering unit of the alkaline electrolyzed water,
the circulating filter unit filters the alkaline electrolyzed water overflowing from the degreasing tank by using a filter unit and then returns the alkaline electrolyzed water to the lower part of the degreasing tank.
In the electrolytic degreasing device of the present invention, the anode electrode is preferably an iridium oxide electrode.
In the electrolytic degreasing device of the present invention, it is preferable that at least an inner surface of the degreasing bath is formed of a material that can reflect ultrasonic waves, and the anode electrode includes a communication portion through which ultrasonic waves can pass.
In the electrolytic degreasing device of the present invention, it is preferable that the hydrogen bubble breaking means is ultrasonic wave irradiation means for irradiating hydrogen bubbles generated on the surface of the object to be cleaned with ultrasonic waves in the alkaline electrolyzed water.
ADVANTAGEOUS EFFECTS OF INVENTION
By using the electrolytic degreasing method and the electrolytic degreasing apparatus of the present invention, even if the object to be cleaned has a complicated surface shape with fine irregularities, the contaminants adhering to the surface can be effectively removed. Furthermore, the oil removed from the surface of the object to be cleaned can be decomposed into carbon and carbon dioxide in the alkaline electrolyzed water, and thus the removed oil does not adhere to the surface of the object to be cleaned again. Therefore, according to the electrolytic degreasing method and the electrolytic degreasing apparatus of the present invention, a cleaning effect which is particularly excellent as compared with the conventional degreasing method and the conventional degreasing apparatus can be obtained.
Drawings
Fig. 1 is a schematic diagram illustrating an embodiment of an electrolytic degreasing apparatus.
Fig. 2 is a schematic view illustrating another embodiment of the electrolytic degreasing apparatus.
Description of the symbols
1 electrolytic degreasing device, 10 degreasing bath, 11 anode electrode, 11a communication part, 12 rectifier (energizing means), 13 ultrasonic irradiation means (ultrasonic irradiation means, hydrogen bubble breaking means), 15 circulation returning port, 16 alkaline electrolyzed water recovery part, 20 rolled steel strip (object to be cleaned), 21 conveying line, 22 hanging part, 23 object to be cleaned, 30 circulation filtering means (circulation filtering means), 31 filter (filtering means), 32 pump, 33 adjusting tank, 34 circulation piping, 35 circulation piping, 36 return piping
Detailed Description
Hereinafter, the embodiments of the present invention will be described in the order of "the embodiment of the electrolytic degreasing method" and "the embodiment of the electrolytic degreasing apparatus".
< method of electrolytic degreasing of the present invention >
The electrolytic degreasing method of the present invention is a method for removing contaminants such as oil adhering to the surface of an object to be cleaned with alkaline electrolytic water. In the present invention, the object to be cleaned and the anode electrode are arranged in the alkaline electrolytic water and energized to cathodically polarize the object to be cleaned, thereby forming hydrogen bubbles having a diameter of 20nm to 10 μm on the surface of the object to be cleaned, the hydrogen bubbles are broken in the vicinity of the surface of the object to be cleaned, and the contaminants adhering to the surface of the object to be cleaned are removed by a shock wave (cavitation) generated by the breaking. Further, the electrolytic degreasing method of the present invention is characterized by comprising an electrode catalyst layer containing 10g/m of an electrode catalyst on the surface of the anode electrode2～20g/m2Iridium oxide in an amount. The electrolytic degreasing method of the present invention will be specifically described below.
Alkaline electrolyzed water: the "alkaline electrolyzed water" used in the present invention is an alkaline aqueous solution obtained by electrolyzing water to which an electrolyte is added in a membrane type electrolytic cell by a predetermined direct current. In view of the problem that micro-nano bubbles of hydrogen are formed on the surface of an object to be cleaned when the object to be cleaned and an anode electrode are placed in alkaline electrolytic water and energized, the alkaline electrolytic water is preferably alkaline electrolytic water to which potassium carbonate and potassium hydroxide are added.
Further, in view of the problem that the oil removed from the surface of the object to be cleaned is decomposed into carbon and carbon dioxide in the alkaline electrolytic water, the alkaline electrolytic water is preferably pH11 to pH 13. When alkaline electrolyzed water having a pH of 11 or more is not used, the effect of alkaline degreasing cannot be sufficiently exhibited, and the production efficiency required in industry cannot be obtained. On the other hand, when alkaline electrolyzed water having a pH exceeding 13 is used, the alkaline degreasing effect is saturated, and chemicals are wasted, which is not preferable.
In addition, when preparing the alkaline electrolyzed water, "alkaline electrolyzed water having a purity of 99.9 mass% or more" is preferably used. This is because, when "alkaline electrolyzed water having a purity of less than 99.9 mass% is used", the degreasing performance fluctuates due to the trace elements contained in the water.
Object to be cleaned: the object to be cleaned mentioned in the present invention is not particularly limited as long as it is immersed in alkaline electrolytic water and a voltage is applied between the object and an anode to form a cathode electrode. Therefore, the object to be cleaned is "a metal product having conductivity", "a plastic plated product having conductivity at least on the surface layer", "a conductive plastic product", or the like. The shape, size, and the like of the object to be cleaned are not particularly limited, and these are not necessarily used.
Hydrogen bubbling: in the present invention, an object to be cleaned and an anode electrode are arranged in alkaline electrolytic water, and electricity is passed between the object to be cleaned and the anode electrode, whereby hydrogen bubbles are formed on the surface of the object to be cleaned, which is cathodically polarized. The hydrogen bubbles are preferably micro-nano bubbles with the bubble diameter of 20 nm-10 mu m. When the bubble diameter is less than 20nm, the bubble diameter is difficult to determine, and is therefore defined as the lower limit. On the other hand, if the bubble diameter exceeds 10 μm, the surface of the object to be cleaned has a fine uneven shape, and the bubble diameter becomes too large and then the bubble hardly enters the concave portion, and a sufficient electrolytic degreasing effect cannot be obtained, which is not preferable.
Here, "micro-nano bubbles" are explained. The "micro-nano bubbles" are terms indicating that "micro bubbles" and "nano bubbles" exist in a mixed state in a solution. "micro-bubbles" generally refer to fine bubbles having a diameter in the range of 1 μm to 10 μm. The "nanobubbles" are finer bubbles than the microbubbles, and bubbles of 1 μm or less in nm are generally called nanobubbles. At this time, the bubbles were extremely fine, and water was produced which could not be visually confirmed and appeared transparent.
The technique for producing nanobubbles has not yet been fully established, and there are adopted "a method of crushing microbubbles", "a method of producing microbubbles with spg (shirasu Porous glass)" and "a method of releasing compressed gas from a membrane having pores with a nano-scale open diameter". In contrast, in the present invention, an object to be cleaned and an anode electrode are arranged in alkaline electrolytic water, and electricity is passed between the object to be cleaned and the anode electrode to electrolytically treat the alkaline electrolytic water, thereby generating "micro-nano bubbles" including "hydrogen nano bubbles" on the surface of the object to be cleaned constituting a cathode electrode. In particular, by adding 2.8g/L or more of potassium carbonate to the alkaline electrolytic water, "micro-nano bubbles" including "hydrogen nano bubbles" can be generated on the surface of the object to be cleaned more effectively.
Further, in addition to the potassium carbonate, potassium hydroxide is preferably added to the alkaline electrolyzed water. Preferably, potassium carbonate and potassium hydroxide are added in combination to the alkaline electrolyzed water so that the total concentration of the both becomes 2.8g/L to 5.6 g/L. When the total concentration of potassium carbonate and potassium hydroxide is less than 2.8g/L, the generation efficiency of hydrogen micro-nano bubbles when the potassium carbonate and potassium hydroxide are added cannot be maintained at a certain level or more. On the other hand, when the total concentration of potassium carbonate and potassium hydroxide exceeds 5.6g/L, the effect of generating hydrogen micro-nano bubbles is saturated, and the waste of chemicals is caused, which is not preferable.
Moreover, it is preferable that the current supply condition in the electrolysis is 5000mA/dm2～15000mA/dm2A range of currents. Using less than 5000mA/dm2The case of (3) is not preferable because the degreasing rate is low and the productivity required for industrial production cannot be satisfied. On the other hand, use is made of more than 15000mA/dm2When the current value of (3) is set to be smaller, the concentration of the current on the convex portion becomes more remarkable and it is difficult to uniformly electrolytically degrease the surface of the object to be cleaned.
Further, the treatment time of the electrolytic treatment is preferably in the range of 3 seconds to 5 seconds. Here, if the treatment time of the electrolytic treatment is less than 3 seconds, it is difficult to sufficiently perform the electrolytic degreasing treatment on the surface of the object to be cleaned, which is not preferable. On the other hand, if the treatment time of the electrolytic treatment exceeds 5 seconds, the electrolytic degreasing ability is saturated, which is not preferable in view of the treatment efficiency.
Occurrence of cavitation: in the present invention, the hydrogen bubbles are broken, so that a cavitation phenomenon occurs in the vicinity of the surface of the object to be cleaned due to the breakage of the hydrogen bubbles, thereby removing contaminants adhering to the surface of the object to be cleaned. Hereinafter, a method of "breaking up hydrogen bubbles" will be described. As described above, in the case of hydrogen bubbles in the micro-nano bubble state, bubbles equivalent to "nano bubbles" do not disappear by air when no external factors such as impact are applied. Therefore, it is preferable that the hydrogen bubbles near the surface of the object to be cleaned are irradiated with ultrasonic waves in the alkaline electrolytic water to "break up the hydrogen bubbles".
When the hydrogen bubbles are broken, the efficiency of removing contaminants such as oil from the surface of the object to be cleaned is greatly improved by the shock wave generated during the breaking. The shock wave generated when the hydrogen bubbles are broken in the cavitation phenomenon is utilized regardless of the shape of the object to be cleaned and the surface condition of the object to be cleaned, and the contaminants can be effectively removed.
Anode electrode: in the electrolytic degreasing method of the present invention, the anode electrode has an electrode catalyst layer on the surface thereof, and the electrode catalyst layer contains 10g/m2～20g/m2Iridium oxide in an amount. Here, the anode electrode of the present invention has an electrode catalyst layer containing 10g/m of an electrolyte on the surface thereof2～20g/m2The durability can be improved by the iridium oxide in an amount, and the electrolytic degreasing effect can be stably achieved for a long period of time. Since the anode electrode of the present invention is an iridium oxide electrode containing iridium oxide as a main component, hydrogen bubble formation and oil decomposition described below are facilitated, and an excellent electrolytic degreasing effect can be obtained.
When the iridium oxide electrode is used as an anode electrode, a "superoxide anion (active oxygen)" having an oxidizing action can be efficiently generated on the surface of the iridium oxide electrode. The "superoxide anion (active oxygen)" oxidizes and decomposes the oil component removed from the object to be cleaned into "carbon" and "carbon dioxide". As a result, the oil floating in the alkaline electrolyzed water disappears, and the removed oil does not adhere to the surface of the object to be cleaned again. At this time, "carbon" is preferably settled in the alkaline electrolyzed water, and the alkaline electrolyzed water is filtered by circulation to maintain a clean state.
< electrolytic degreasing apparatus of the invention >
The electrolytic degreasing apparatus of the present invention is an electrolytic degreasing apparatus for cleaning a surface of an object to be cleaned by the above-described electrolytic degreasing method, and includes a degreasing tank for storing alkaline electrolytic water, an anode electrode disposed in the degreasing tank, an energizing means for performing cathodic polarization by disposing the object to be cleaned in a state of being immersed in the alkaline electrolytic water, and a breaking means for breaking hydrogen bubbles near the surface of the object to be cleaned. In the electrolytic degreasing apparatus of the present invention, the circulation filter unit filters the alkaline electrolyzed water overflowing from the degreasing tank by the filter unit, and returns the filtered alkaline electrolyzed water to the lower part of the degreasing tank. The electrolytic degreasing apparatus according to the present invention will be described in detail below with reference to the drawings.
Fig. 1 is a schematic diagram illustrating an embodiment of an electrolytic degreasing apparatus. The object to be cleaned in the present embodiment is a rolled steel strip 20 with contaminants such as oil remaining on the surface. The electrolytic degreasing apparatus 1 according to the present invention includes a degreasing bath 10 for storing alkaline electrolytic water, anode electrodes 11,11 immersed in the alkaline electrolytic water, a rectifier 12 as a current-carrying means, and an ultrasonic irradiation device (ultrasonic irradiation means) 13 as a breaking means for hydrogen bubbles near the surface of a rolled steel strip 20 immersed in the alkaline electrolytic water.
Alkaline electrolytic water is stored in the degreasing tank 10. The alkaline electrolyzed water of the present embodiment is usually used as an electrolyzed water production apparatus for producing alkaline electrolyzed water. The alkaline electrolyzed water is an alkaline electrolyzed water obtained within at least 48 hours from the time of generation of the electrolyzed water, and potassium carbonate and potassium hydroxide are added to the alkaline electrolyzed water at a predetermined concentration.
The anode 11 is disposed and used by immersing at least two electrodes in alkaline electrolytic water in a state of facing each other with a predetermined dimension therebetween. In this case, in the present embodiment, the anodes are arranged substantially in parallel and facing each otherElectrodes 11, 11. As in the case of the electrolytic degreasing method described above, each of the anode electrodes 11,11 is preferably an iridium oxide electrode containing iridium oxide as a main component, and more preferably has a surface containing 10g/m of iridium oxide2～20g/m2An electrode catalyst layer of iridium oxide in an amount.
In the electrolytic degreasing apparatus of the present invention, at least the inner surface of the degreasing bath 10 is preferably formed of a material that reflects ultrasonic waves, and the anode electrode 11 is preferably provided with a communicating portion through which ultrasonic waves can pass. Here, when the anode electrode 11 includes the communicating portion, the traveling direction of the ultrasonic wave is reflected in the degreasing bath 10 without being obstructed by the anode electrode 11, and the hydrogen bubbles near the surface of the rolled steel strip 20 are promoted to be broken. For example, as shown in fig. 2, it is preferable to form the anode electrode 11 from a plate material having a mesh-like communicating portion 11a or a punched hole to have the communicating portion 11a, thereby improving the transmittance of the ultrasonic wave. In the present invention, it is more preferable that the anode electrode 11 is formed of a wire mesh and has the communicating portion 11a because the transmittance of ultrasonic waves can be further improved. Further, since the inner surface of the degreasing bath 10 is made of stainless steel, the ultrasonic waves irradiated in the alkaline electrolytic water can be effectively amplified, and the breaking of hydrogen bubbles in the vicinity of the surface of the object to be cleaned can be further promoted.
In the present embodiment, the rolled steel strip 20 travels from one direction (the drawing portion side) to the other direction (the coiling portion side) by the drawing portion and the coiling portion (not shown) constituting the traveling means. The rolled steel strip 20 drawn out from the drawing section is wound around the winding section after running between the anode electrodes 11,11 disposed in the alkaline electrolytic water in the degreasing bath 10. Therefore, the rolled steel strip 20 is positioned between the anode electrodes 11,11 disposed to face each other in the alkaline electrolytic water, and is disposed to be spaced apart from the respective anode electrodes 11,11 by a predetermined dimension.
In order to sufficiently ensure the time for the electrolytic degreasing treatment of the surface of the rolled steel strip 20, the degreasing bath 10 is preferably formed long in the traveling direction of the rolled steel strip 20, and similarly, the anode electrodes 11,11 immersed in the alkaline electrolytic water in the degreasing bath 10 are also preferably formed long in the traveling direction of the rolled steel strip 20. Fig. 1 shows a schematic sectional view when viewed from the drawing-out portion side or the winding portion side.
Further, positive charges are applied to the anode electrodes 11,11 by a rectifier 12 as a current applying means, and negative charges are applied to the rolled steel strip 20.
In the degreasing tank 10, an ultrasonic irradiation device 13 is disposed below a position corresponding to the running of the rolled steel strip 20. The ultrasonic irradiation device 13 is a means for irradiating the hydrogen bubbles generated near the surface of the rolled steel strip 20 with 35Hz to 45Hz ultrasonic waves based on the energization of the rolled steel strip 20, and in the present embodiment, a device outputting 100W is used. In the present embodiment, the ultrasonic irradiation device 13 is disposed on the bottom surface of the degreasing bath 10, but the arrangement position is not limited thereto, and any position may be used as long as the ultrasonic irradiation device can irradiate the vicinity of the surface of the rolled steel strip 20 to which negative charges are applied.
Fig. 1 shows a case where the degreasing bath 10 is provided with a circulation filter mechanism (circulation filter means) 30 for alkaline electrolyzed water. The circulation filtration mechanism 30 includes at least a filter 31 as a filtration unit, and a pump 32 for conveying the alkaline electrolyzed water in the degreasing bath 10 to the filter 31. In the present embodiment, an alkaline electrolyzed water recovery unit 16 for circulating and filtering the alkaline electrolyzed water in the degreasing bath 10 is formed at a height position near the liquid surface of the alkaline electrolyzed water in the degreasing bath 10, and a circulation pipe 34 is connected to the alkaline electrolyzed water recovery unit 16. The other end of the circulation pipe 34 is connected to the filter 31, and the pump 32 is connected to the filter 31 via the circulation pipe 35. The pump 32 is connected to a conditioning tank 33, and the conditioning tank 33 is connected to a circulation return port 15 for returning the filtered alkaline electrolyzed water to the degreasing tank 10 via a circulation pipe 36. In the present embodiment, the filter 31 is made of polypropylene.
With the above configuration, the operation of the electrolytic degreasing apparatus 1 according to the present embodiment will be described. First, the running means is operated to run the rolled strip 20 as the object to be cleaned from the drawing portion side to the winding portion side. Subsequently, positive charges are applied to each of the anode electrodes 11,11 immersed in the alkaline electrolytic water by the rectifier 12, and negative charges are applied to the rolled steel strip 20.
Thereby, the alkaline electrolytic water in the degreasing bath 10 is electrolyzed, and "micro-nano bubbles" including "hydrogen nano bubbles" are generated on the surface of the rolled steel strip 20 constituting the cathode electrode. Here, the ultrasonic wave is irradiated to the vicinity of the surface of the rolled steel strip 20 by the ultrasonic wave irradiation device 13. Thus, "hydrogen bubbles" containing "micro-nano bubbles" formed near the surface of the rolled steel strip 20 are broken by the ultrasonic waves, the breaking of the hydrogen bubbles causes a cavitation phenomenon, and contaminants attached to the surface of the rolled steel strip 20 are removed from the surface of the rolled steel strip 20.
On the other hand, as the alkaline electrolytic water in the electrolytic degreasing bath 10 is electrolyzed, oxygen bubbles are generated on the surfaces of the anode electrodes 11, 11. At this time, since the anode electrode is an iridium oxide electrode as described above, oxygen generated on the surface of the anode electrode 11 is decomposed, and superoxide anions (active oxygen) are efficiently generated. In the vicinity of the surface of the anode electrode 11, the generated superoxide anions (active oxygen) diffuse into the alkaline electrolytic water in the degreasing bath 10, react with contaminants such as oil separated and removed from the surface of the rolled steel strip 20, and oxidize and decompose the oil into carbon and carbon dioxide.
The decomposed carbon dioxide is released as a gas into the atmosphere for disposal. On the other hand, when the pump 32 of the circulation filter mechanism 30 is operated, the alkaline electrolyzed water containing carbon reaches the filter 31 from the alkaline electrolyzed water recovery unit 16 formed at a height position near the liquid surface of the alkaline electrolyzed water in the degreasing bath 10 through the circulation pipe 34. The carbon in the alkaline electrolyzed water is adsorbed and removed by the filter 31, and the alkaline electrolyzed water from which the carbon is removed is returned from the circulation return port 15 into the degreasing tank 10 via the circulation pipe 35, the pump 32, and the adjustment tank 33.
According to the electrolytic degreasing apparatus 1 of the present invention, since hydrogen nanobubbles having a diameter of 20nm to 10 μm are generated on the surface of the rolled steel strip 20 subjected to the cathodic polarization, even when the surface shape of the rolled steel strip 20 is complicated, the hydrogen nanobubbles having a diameter of 20nm to 10 μm may be caused to enter the recesses of the surface shape. The hydrogen nanobubbles entered into the concave portion are irradiated with ultrasonic waves and then are crushed, and contaminants such as oil adhering to the concave portion can be effectively removed by a shock wave generated by the crushing. Thus, a cleaning effect which is remarkably superior to that of the conventional alkaline degreasing method can be obtained.
Further, according to the electrolytic degreasing apparatus 1 of the present invention, the contaminants such as oil components separated and removed from the surface of the rolled steel strip 20 are oxidized by "superoxide anions (active oxygen)" generated on the surface of the anode electrode at the time of electrolysis of the alkaline electrolytic water, and decomposed into "carbon" and "carbon dioxide". Since carbon is precipitated in the alkaline electrolytic water, the electrolytic degreasing device 1 of the present invention may be provided with a precipitation filter mechanism (not shown). At this time, the carbon deposited by the filtration treatment of the deposition filtration means is removed, and carbon dioxide is released from the alkaline electrolyzed water to the atmosphere. Thus, contaminants such as oil separated and removed from the surface of the rolled steel strip 20 are effectively decomposed and removed, and the problem of re-adhesion to the surface of the rolled steel strip 20 can be avoided.
In the above-described embodiment, the long rolled steel strip 20 wound in a roll shape is pulled out from one direction and wound in the other direction, but the object to be cleaned in the present invention is not limited to this. For example, as shown in fig. 2, a plurality of hanging members 22 may be provided at predetermined intervals on the conveying line 21 constituting the traveling unit, and the object 23 to be cleaned may be detachably attached to the lower ends of the hanging members 22. In addition, the object to be cleaned of the present invention may be a plate-like object that cannot be wound up, as long as the object is moved from one direction to the other direction by the moving means.
Industrial applicability
According to the electrolytic degreasing method of the present invention, the surface of the object to be cleaned can be effectively cleaned and treated, and the subsequent formation of the plating film can be favorably performed, and the electrolytic degreasing method is applicable to all products requiring degreasing treatment. In particular, it is suitable for cleaning the surface of a product to be plated. By using the electrolytic degreasing method of the present invention, contaminants can be effectively removed from the surface of a plating object having complicated fine irregularities, and the removed oil component is prevented from adhering to the surface of the object to be cleaned again, whereby a plating layer having good quality can be formed.
Further, the electrolytic degreasing apparatus of the present invention does not require a special structure, and the apparatus design is easy. Further, the electrolytic degreasing apparatus of the present invention can be easily incorporated into a continuous production line such as a plating line or a vacuum deposition line, and can continuously clean and treat the object to be cleaned, thereby realizing the production of a final product.

Claims (7)

1. An electrolytic degreasing method for removing oil adhering to the surface of an object to be cleaned with alkaline electrolytic water,
an object to be cleaned and an anode electrode are arranged in alkaline electrolytic water and energized, and the object to be cleaned is cathodically polarized to form hydrogen bubbles having a diameter of 20nm to 10 μm on the surface of the object to be cleaned, the hydrogen bubbles are broken in the vicinity of the surface of the object to be cleaned, oil adhering to the surface of the object to be cleaned is removed by a shock wave generated by the breaking,
the anode electrode has an electrode catalyst layer containing 10g/m on the surface thereof immersed in the alkaline electrolyzed water2～20g/m2Iridium oxide in an amount.
2. The electrolytic degreasing method as claimed in claim 1, wherein the alkaline electrolytic water is an aqueous solution containing potassium carbonate and potassium hydroxide and having a pH of 11-13.
3. The electrolytic degreasing method as claimed in claim 1 or 2, wherein the hydrogen bubbles near the surface of the object to be cleaned are broken by irradiating the hydrogen bubbles with ultrasonic waves in alkaline electrolyzed water.
4. The electrolytic degreasing method as claimed in claim 1 or 2, wherein the superoxide anion generated at the anode electrode during energization and the oil removed from the surface of the object to be cleaned are reacted in the alkaline electrolytic water, thereby decomposing the oil into carbon and carbon dioxide.
5. An electrolytic degreasing apparatus for cleaning a surface of an object to be cleaned by the electrolytic degreasing method as set forth in any one of claims 1 to 4, comprising
A degreasing tank for storing alkaline electrolyzed water,
an electrode catalyst layer disposed in the degreasing tank and having a surface immersed in the alkaline electrolyzed water, the electrode catalyst layer containing 10g/m2～20g/m2An anode electrode of an amount of iridium oxide,
an energizing means for forming hydrogen bubbles having a diameter of 20nm to 10 μm on the surface of the object to be cleaned by placing the object to be cleaned in the alkaline electrolytic water in a state of being immersed and cathodically polarizing the object to be cleaned,
a hydrogen bubble breaking unit for breaking the hydrogen bubbles near the surface of the object to be cleaned, and
the circulation filtering unit of the alkaline electrolyzed water,
the circulating filter unit filters the alkaline electrolyzed water overflowing from the degreasing tank by using a filter unit and then returns the alkaline electrolyzed water to the lower part of the degreasing tank.
6. The electrolytic degreasing apparatus as claimed in claim 5, wherein at least an inner surface of the degreasing bath is formed of a material that reflects ultrasonic waves, and the anode electrode has a communication portion through which ultrasonic waves can pass.
7. The electrolytic degreasing apparatus as claimed in claim 5 or 6, wherein the hydrogen bubble breaking means is an ultrasonic wave irradiation means for irradiating hydrogen bubbles generated on the surface of the object to be cleaned with ultrasonic waves in alkaline electrolyzed water.
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Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109482560A (en) * 2018-11-30 2019-03-19 江阴精力机械有限公司 Automatic spray paint production line high-efficiency cleaning pretreatment unit and its pretreating process
TWI691358B (en) * 2019-03-04 2020-04-21 日商長瀨過濾器股份有限公司 Filter cleaning method and filter cleaning device
JP7406748B2 (en) 2019-06-12 2023-12-28 国立大学法人九州工業大学 chemical plating method
CN110404871B (en) * 2019-08-05 2021-11-30 宁波凯达橡塑工艺有限公司 Self-cleaning corneal contact lens cleaner
CN111297046A (en) * 2019-11-02 2020-06-19 桐城市桃花制刷有限公司 Preparation method of paint brush
CN110679824A (en) * 2019-11-06 2020-01-14 西华大学 Fresh noodle preservative and preparation method thereof
CN112553680B (en) * 2020-11-06 2021-10-22 福耀汽车铝件(福建)有限公司 Method for stripping electrophoretic coating on surface of hanger
CN116103741A (en) * 2021-04-06 2023-05-12 重庆立道新材料科技有限公司 Descaling device
CN116371804B (en) * 2023-04-07 2023-12-05 南通大学 Silicon waste cleaning device and cleaning method

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1541285A (en) * 2001-02-06 2004-10-27 美国过滤公司 Electrode coating and its use in prodn. of chlorate
CN101532147A (en) * 2009-02-26 2009-09-16 中国船舶重工集团公司第七二五研究所 Nanocrystal metal oxide composite electrode and method for preparing same
CN104797742A (en) * 2012-09-21 2015-07-22 Ucl商业有限公司 Electrolysis electrocatalyst

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59103761U (en) * 1982-12-27 1984-07-12 中井　俊晴 Oil removal device used in degreasing tanks, etc.
JPS59123797A (en) * 1982-12-28 1984-07-17 Mitsubishi Heavy Ind Ltd Electrode used for surface treatment of band sheet
JPH02274900A (en) * 1989-04-15 1990-11-09 Toto Ltd Method for removing heavy metal
JP3213833B2 (en) * 1994-01-31 2001-10-02 ダイソー株式会社 Electrolytic pickling method for stainless steel plate and electrode used for it
JPH10245700A (en) * 1997-03-04 1998-09-14 Shibafu Eng Kk Method for degreasing and washing conductive member and method for degreasing and washing piping
JP4171053B2 (en) * 2007-03-22 2008-10-22 ソマックス株式会社 Electrolytic cleaning device
JP6000058B2 (en) * 2012-10-23 2016-09-28 札内工業株式会社 Electrolytic degreasing method and electrolytic degreasing apparatus

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1541285A (en) * 2001-02-06 2004-10-27 美国过滤公司 Electrode coating and its use in prodn. of chlorate
CN101532147A (en) * 2009-02-26 2009-09-16 中国船舶重工集团公司第七二五研究所 Nanocrystal metal oxide composite electrode and method for preparing same
CN104797742A (en) * 2012-09-21 2015-07-22 Ucl商业有限公司 Electrolysis electrocatalyst

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