CN100378247C - Acid washing device - Google Patents
Acid washing device Download PDFInfo
- Publication number
- CN100378247C CN100378247C CNB200510067320XA CN200510067320A CN100378247C CN 100378247 C CN100378247 C CN 100378247C CN B200510067320X A CNB200510067320X A CN B200510067320XA CN 200510067320 A CN200510067320 A CN 200510067320A CN 100378247 C CN100378247 C CN 100378247C
- Authority
- CN
- China
- Prior art keywords
- pickling
- particle
- frequency
- pickle solution
- ultrasonic oscillator
- 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 - Fee Related
Links
Images
Classifications
-
- 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
- C23G3/02—Apparatus for cleaning or pickling metallic material for cleaning wires, strips, filaments continuously
-
- 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
- C23G1/36—Regeneration of waste pickling liquors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B45/00—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills
- B21B45/02—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills for lubricating, cooling, or cleaning
- B21B45/0269—Cleaning
- B21B45/0275—Cleaning devices
- B21B45/0287—Cleaning devices removing solid particles, e.g. dust, rust
-
- 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
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/08—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
- C23G3/02—Apparatus for cleaning or pickling metallic material for cleaning wires, strips, filaments continuously
- C23G3/021—Apparatus for cleaning or pickling metallic material for cleaning wires, strips, filaments continuously by dipping
-
- 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
- C23G3/02—Apparatus for cleaning or pickling metallic material for cleaning wires, strips, filaments continuously
- C23G3/025—Details of the apparatus, e.g. linings or sealing means
-
- 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
- C23G3/02—Apparatus for cleaning or pickling metallic material for cleaning wires, strips, filaments continuously
- C23G3/027—Associated apparatus, e.g. for pretreating or after-treating
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
The pickling equipment equipped with a pickling tank 3 for performing pickling of the steel sheet 1 containing silicon by successively passing the steel sheet 1 and a circulating route 5 for circulating the pickling solution in the pickling tank 3 is provided with ultrasonic vibrator transducers 10, 14 and 18 which oscillate ultrasonic waves of different frequencies f 1, f 2, and f 3 to the pickling solution circulating in the circulating route at separation tanks 9, 13 and 17 such that the SiO<SB>2</SB>particles of the grain sizes different from each other of the respective frequencies f 1, f 2, an f 3 are removed by flocculation and settlement. Thus, SiO<SB>2</SB>particles in a pickling solution generated during pickling of various silicon steel sheets can be decreased, and long-term operation and the period of maintenance work can be prolonged and productivity is high.
Description
Technical field
The present invention relates to a kind of pickling installation that recycles pickle solution and steel plate is carried out pickling.
Background technology
In the manufacturing process of steel plate, after temporary transient the coiling, it is waited without cool off the steel plate after the operations such as hot rolling, thereafter it is untied and carry out cold rolling etc.In this refrigerating work procedure, can produce oxide skin as oxide compound at surface of steel plate.Therefore, before cold rolling grade,, carry out cleanup acid treatment for this oxide skin is removed.So-called cleanup acid treatment is meant, makes at steel plate for example formed oxide skin and pickle solution generation chemical reactions such as hydrochloric acid or nitric acid on the surface of steel plate of the processing steel plate of cold-rolled steel sheet or hot-rolled steel sheet and so on, and the processing that oxide skin is removed.Pickling 0.74 equipment in the manufacturing process of steel plate is the equipment that is provided with in order to carry out this cleanup acid treatment.
The acid washing method that utilizes pickling installation to carry out in the past is to pass through steel plate in a plurality of pickling tanks continuously, the method that steel plate is immersed in store in the pickle solution in pickling tank and oxide skin is removed, or steel plate is passed through in a plurality of pickling tanks continuously, the method for in pickling tank, removing to the surface of steel plate ejection pickle solution and with oxide skin.
This kind pickling installation in the past for example is disclosed in the patent documentation 1 to 3.
Patent documentation 1:(Japan) No. 3064080 communique of patent
Patent documentation 2:(Japan) No. 3322965 communique of patent
Patent documentation 3:(Japan) spy opens flat 5-195268 communique
In the production of in recent years steel plate, except general steel plate, also to produce the different various silicon steel sheets of silicone content and contain the special steel plate of more silicon, for example electro-magnetic steel plate or Trip steel plate etc.In that this kind silicon steel sheet and the special steel plate that contains more silicon are carried out under the situation of pickling, have the situation of silicon Si from surface stripping to pickle solution of steel plate, in addition, also have the situation of silicon Si stripping from the oxide skin of having removed.
When silicon steel sheet and the special steel plate that contains more silicon are carried out pickling, the silicon Si of stripping can with the oxygen O in the pickle solution
2Reaction becomes silicon-dioxide SiO in pickle solution
2Contain the SiO that constitutes by this particulate when making
2The pickle solution of composition when the pickling installation internal recycle, SiO
2Particle becomes gel, is trapped in tank body in the equipment or pipe arrangement etc.In addition, in pickling installation, has the heat exchanger that pickle solution is remained on proper temperature, gelatinous SiO
2Particle particularly causes obstruction in this heat exchanger that has than tubule, and securely attached on the heat-transfer surface.Like this, not only can make pickle solution circulation bad, and can produce the reduction of heat transfer property of heat exchanger or obstruction etc., thereby cause dysfunction.
Because SiO
2Particle forms densification and chemically stable oxide skin, therefore when in equipment, be detained or attached to machines such as heat exchangers on the time, removing of it just has to rely on mechanical operation.With the gelatinous SiO of this kind
2Under the situation that particle is removed, the cleaning of equipment etc. is carried out in the running of arrestment for a long time, and operation and maintenance are produced very big detrimentally affect, also becomes the essential factor that reduces production efficiency.
But, in described pickling installation in the past,, also do not take any countermeasure for producing in the pickle solution after cleanup acid treatment and the running of equipment being caused dysgenic particulate.In addition, the particulate in the oxide skin that suspends in pickle solution can shorten the life-span of pickle solution, also becomes the reason of the quality that reduces steel plate.
Summary of the invention
The objective of the invention is to solve described problem, the pickling installation in the high pickling of a kind of following production efficiency is provided, it can reduce particulate contained in the pickle solution, particularly reduces the SiO in the pickle solution that produces when the pickling of various silicon steel sheets
2Particle, thus can operate and prolong the cycle of maintenance for a long time.
The pickling installation that solves one of the present invention of described problem be possess steel plate materials successively the pickling by carrying out this steel plate materials pickling tank, make the pickling installation of the pickle solution round-robin circulating path in the described pickling tank, it is characterized in that, to the ultrasonic wave of a plurality of different frequencies of the irradiation of round-robin pickle solution multistage ground in described circulating path, under each frequency, make particle coagulation, the precipitation of different-grain diameter.
The present invention's two the pickling installation that solves described problem is in one of the present invention's pickling installation, possesses following feature, that is, the separator tank of separating particles from pickle solution is set on described circulating path, on described separator tank, has possessed the hyperacoustic ultrasonic oscillator that sends different frequency.
The present invention's three the pickling installation that solves described problem is in the present invention's two pickling installation, possesses following feature, promptly, on the sidewall of described separator tank, reflector is set, the distance of integral multiple of half-wavelength that described reflector and described ultrasonic oscillator is configured in the frequency of being set by described ultrasonic oscillator is last, and the sidewall of described separator tank is made with low density material.
The present invention's four the pickling installation that solves described problem is in the pickling installation of one of the present invention any one in to three, possesses following feature, that is, described ultrasonic wave is set to high frequency ground from low frequency by from the upstream side of described circulating path side downstream interimly.
The present invention's five the pickling installation that solves described problem is in the pickling installation of one of the present invention any one in to three, possesses following feature, that is, described ultrasonic wave is set to low frequency ground from high frequency by from the upstream side of described circulating path side downstream interimly.
The present invention's six the pickling installation that solves described problem is in the present invention's four or five pickling installation, possesses following feature, that is, the cohesion zone of the frequency of being set by described each ultrasonic oscillator is set according to the mode that contains the particle size region of cohesion, sedimentary particulate from pickle solution.
The present invention's seven the pickling installation that solves described problem is in the pickling installation of one of the present invention any one in to six, possesses following feature, promptly, the described steel plate materials of the described pickling tank by carrying out pickling is the steel plate materials that contains silicon successively, and each ultrasonic wave is condensed, the particulate in the sedimentary pickle solution is SiO
2Particle.
The present invention's eight the pickling installation that solves described problem possesses following feature in the pickling installation of one of the present invention any one in to seven, that is, cohesion, the particulate that precipitated are reclaimed.
Pickling installation one of according to the present invention, possessed steel plate materials successively the pickling by carrying out this steel plate materials pickling tank, make the pickling installation of pickle solution round-robin circulating path in the described pickling tank, because by ultrasonic wave to a plurality of different frequencies of the irradiation of round-robin pickle solution multistage ground in described circulating path, make particle coagulation, the precipitation of different-grain diameter under each frequency, just can operate and prolong the cycle of maintenance for a long time.In addition, owing to can remove particulate, therefore can obtain high efficiency with not stopping pickling installation.
Two pickling installation according to the present invention, in one of the present invention's pickling installation, by the separator tank of separating particles from pickle solution is set on described circulating path, on described separator tank, be provided with the hyperacoustic ultrasonic oscillator that sends different frequency, just can be reliably from pickle solution with particle coagulation, precipitation.
Three pickling installation according to the present invention, because in the present invention's two pickling installation, by on the sidewall of described separator tank, reflector being set, the distance of integral multiple of half-wavelength that described reflector and described ultrasonic oscillator is configured in the frequency of being set by described ultrasonic oscillator is last, and the sidewall of described separator tank is made with low density material, just can prevent that ultrasonic wave from seeing through the sidewall of described separator tank and decay, therefore just can carry out cohesion, the precipitation of particulate expeditiously.
Four pickling installation according to the present invention, in the pickling installation of one of the present invention any one in to three, by with described ultrasonic wave from the upstream side of described circulating path downstream side set to high frequency ground from low frequency interimly, just can interimly condense effectively, precipitate to the particulate of small particle size from the particulate of big particle diameter.
Five pickling installation according to the present invention, in the pickling installation of one of the present invention any one in to three, by with described ultrasonic wave from the upstream side of described circulating path downstream side set to low frequency ground from high frequency interimly, just can interimly condense effectively, precipitate to the particulate of big particle diameter from the particulate of small particle size.
Six pickling installation according to the present invention, in the present invention's four or five pickling installation, cohesion zone by the frequency that will be set by described each ultrasonic oscillator is set according to the mode that contains the particle size region of cohesion, sedimentary particulate from pickle solution, just can further reduce the particulate that suspends in pickle solution.
Seven pickling installation according to the present invention, in the pickling installation of one of the present invention any one in to six, the described steel plate materials of the described pickling tank by carrying out pickling is the steel plate materials that contains silicon successively, even each ultrasonic wave is condensed, the particulate in the sedimentary pickle solution is SiO
2Particle, because in the pickling installation in pickling, the SiO in the pickle solution that when the pickling of various silicon steel sheets, produces
2Particle reduces, and therefore just can operate and prolong the cycle of maintenance for a long time.In addition, owing to can remove SiO with not stopping pickling installation
2Therefore particle can obtain high efficiency.
According to the present invention eight, in the pickling installation of one of the present invention any one in to seven, by will condense, sedimentary particulate reclaims, and just can remove particulate from pickle solution.
Description of drawings
Fig. 1 is the sketch chart of the pickling installation of embodiments of the invention 1.
Fig. 2 is cohesion, the scatter diagram of relation of the particle diameter of expression ultrasonic frequency and particulate.
Fig. 3 be the expression embodiments of the invention 1 pickle solution in SiO
2The figure of the rate of removing of particle.
Fig. 4 is the stereographic map of the tripping device of embodiments of the invention 2.
Fig. 5 is expression other the SiO of embodiment of the present invention
2The sketch chart of the method for removing of particle.
Among the figure: 1-steel plate, 2-steel plate acid-washing device, 3-pickling tank, the 4-cylinder, the 5-circulating path, 5a-relief outlet, 6,7,8, the 21-tripping device, 9,13,17, the 22-separator tank, 9a, 13a, 17a, 22a～22d-sidewall, 9b, 13b, 17b, the 22e-rake, 9c, 13c, 17c, the 22f-relief outlet, 10,14,18,23,24, the 25-ultrasonic oscillator, 11,15,19,26,27, the 28-reflector, 12,16, the 20-relief valve, the 29-influx, the 30-spout, 31, the 32-division plate, 33-grid, 34-ultrasonic oscillator, the 35-relief outlet, f1～f6-frequency.
Embodiment
To be elaborated to pickling installation of the present invention based on embodiment below.
[embodiment 1]
Fig. 1 is the sketch chart of the pickling installation of embodiments of the invention 1.Fig. 2 is cohesion, the scatter diagram of relation of the particle diameter of expression ultrasonic frequency and particulate.Fig. 3 be the expression embodiments of the invention 1 pickle solution in SiO
2The figure of the rate of removing of particle.
As shown in Figure 1, supplied with to the direction of arrow A shown in this figure as the steel plate 1 of the steel plate materials that contains silicon, by the inside of steel plate acid-washing device 2.Steel plate acid-washing device 2 possess store to steel plate 1 carry out the pickle solution of cleanup acid treatment pickling tank 3, be used for the cylinder 4 that pickle solution cuts branch.Pickling tank 3 is communicated with making pickle solution round-robin circulating path 5, pickle solution in this circulation path 5 to flowing in the opposite direction with the supplying party of steel plate 1.At this moment, pickling tank includes the SiO of stripping from steel plate 1
2Particle, the arrow B 1～B4 with this figure represents with the loop direction of pickle solution.
On circulating path 5, begin to be provided with tripping device 6,7,8 from pickle solution institute round-robin upstream side.Tripping device 6 possesses and is used for separating SiO from pickle solution
2The separator tank 9 of particle, be submerged in the pickle solution that stores in separator tank 9 and send hyperacoustic ultrasonic oscillator 10 of frequency f 1.Separator tank 9 has the approximate cone shape rake 9b that forms sidewall 9a cylindraceous, is formed at the bottom of sidewall 9a, the relief outlet 9c that is formed at the bottom of rake 9b.
Similarly, tripping device 7 possesses separator tank 13, sends hyperacoustic ultrasonic oscillator 14 of frequency f 2, and separator tank 13 has sidewall 13a, rake 13b and relief outlet 13c.Sidewall 13a is made by low density material, for example foamed styrene etc., and side is provided with reflector 15 within it.Ultrasonic oscillator 14 is configured in the central part of sidewall 13a, and the distance of this reflector 15 and ultrasonic oscillator 14 is retained as the integral multiple of the half-wavelength of the frequency f of being set by ultrasonic oscillator 14 2.In addition, on relief outlet 13c, be provided with open and close valve 16.
Similarly, tripping device 8 possesses separator tank 17, sends hyperacoustic ultrasonic oscillator 18 of frequency f 3, and separator tank 17 has sidewall 17a, rake 17b and relief outlet 17c.Sidewall 17a is made by low density material, for example foamed styrene etc., and side is provided with reflector 19 within it.Ultrasonic oscillator 18 is configured in the central part of sidewall 17a, and the distance of this reflector 19 and ultrasonic oscillator 18 is retained as the integral multiple of the half-wavelength of the frequency f of being set by ultrasonic oscillator 18 3.In addition, on relief outlet 17c, be provided with open and close valve 20.Frequency f 1, f2, the f3 of each ultrasonic oscillator 10,14,18 are set to f1＜f2＜f3.
Here, around the particle in being suspended in liquid, be attached with the negatively charged ion that is present in the liquid.Owing to repel mutually between the negatively charged ion, so also repel mutually between the particle.But, with it differently, also can attract each other between the particle because of the gravitation of having deferred to the law of universal gravitation.That is, in the particle in liquid, defer to the stronger side of repulsive force and gravitational equilibrated, repel sometimes, attract each other sometimes and merge (cohesion).
As shown in Figure 2; in addition when flowing through ultrasonic wave on the particulate in liquid; particulate can have particle size region of vibrating well with the frequency of ultrasonic response (cohesion zone) and the particle size region (discrete areas) that is difficult to vibrate because of the size of particle diameter, with the different particle size range differences of condensing of frequency.Vibrate intensely with the particle of the particle diameter of frequency match, between particle, carry out repeatedly away from, close, away from, the close process, then attract to condense when interior when approaching to certain distance between the particle together.According to this situation, if the particle size region in the clear liquid that will make it to condense then can be selected the ultrasonic frequency zone that is used to condense.That is, frequency and particle diameter are set accordingly.
Utilize this characteristic, pickling installation of the present invention is by suitable frequency of ultrasonic is provided, at the SiO as the object particulate that suspends in pickle solution
2Excite in the particle size region of particle, make between the particle vibration, ballistic equipment intensely.Consequently, condense between the particle, the diameter of particle that has condensed increases to can sedimentary particle size region, thereby can make SiO
2Particle precipitation.
The SiO of stripping in pickle solution
2When the particle size region of particle for example was made as 1.0～10.0 μ m, if 3 kinds of frequencies of minimum irradiation, then can predict can be according to making SiO
2The mode of the particle size region cohesion of particle contains.So therefore pickling installation of the present invention will carry out to 3 stages SiO owing to possess 3 ultrasonic oscillators 10,14,18
2The cohesion of particle, precipitation are removed.
For example, the frequency f of ultrasonic oscillator 10 is made as 10kHz, the frequency f 2 of ultrasonic oscillator 14 is made as 70kHz, the frequency f 3 of ultrasonic oscillator 18 is made as 500kHz.Particle diameter is about 6.5～16.0 μ m in the cohesion zone under the frequency 10kHz, and particle diameter is about 2.5～6.5 μ m in the cohesion zone under the frequency 70kHz, and particle diameter is about 0.9～2.5 μ m in the cohesion zone under the frequency 500kHz.That is, the cohesion zone of each frequency of being set by ultrasonic oscillator 10,14,18 can be contained as SiO
21.0～10.0 μ m of the particle size region of particle
So, by forming described formation, steel plate 1 is supplied with to steel plate acid-washing device 2, in pickling tank 3, utilize pickle solution to carry out cleanup acid treatment.Carried out pickle solution cleanup acid treatment after and flowed out the separator tank 9 of inflow separation device 6 to circulating path 5 thereafter.The pickle solution that stores in separator tank 9 is arrived tens of seconds by the frequency several seconds of ultrasonic oscillator 10 irradiation 10kHz.At this moment, reflector 11 and ultrasonic oscillator 10 are owing to the distance of the integral multiple of the half-wavelength that is configured in the frequency 10kHz that is set by ultrasonic oscillator 10 is last, and sidewall 9a is made by the foamed styrene of low density material etc., just can prevent that therefore ultrasonic wave from seeing through the sidewall 9a of separator tank 9 and decay.
In addition, the only particle diameter in the pickle solution is about the SiO of 6.5～16.0 μ m
2Between the particle repeatedly intensely the vibration, ballistic simultaneously the cohesion.The SiO that has condensed
2Particle will precipitate when increasing to certain certain particle diameter.Sedimentary SiO
2Particle has rake 9b because of separator tank 9, and precipitates reposefully towards relief outlet 9c, is removed from relief outlet 9c.The SiO that from relief outlet 9c, discharges
2Particle is sent to not shown particulate retrieving arrangement etc.The SiO that arrow C 1 expression of this figure is reclaimed
2Flowing of particle.At this moment, relief valve 12 both can be the state of always opening, and in addition, also can be made as from closing condition and began at SiO
2Particle forms open mode with near back remaining in relief outlet 9c to a certain degree.
Then, utilize the driving of not shown pump etc., the pickle solution of the supernatant liquor of separator tank 9 is fed circulating path 5, make it the separator tank 13 of inflow separation device 7.The pickle solution that stores in separator tank 13 is arrived tens of seconds by the frequency several seconds of ultrasonic oscillator 14 irradiation 70kHz, and the only particle diameter in the pickle solution is about the SiO of 2.5～6.5 μ m
2Between the particle repeatedly intensely the vibration, ballistic simultaneously the cohesion.In addition, as the SiO that has condensed
2When increasing to certain certain particle diameter, removes on particle with regard to precipitated.The SiO that arrow C 2 expressions of this figure are reclaimed
2Flowing of particle.
In addition, utilize the driving of not shown pump etc., the pickle solution of the supernatant liquor of separator tank 13 is fed circulating path 5, make it the separator tank 17 of inflow separation device 8.The pickle solution that stores in separator tank 17 is arrived tens of seconds by the frequency several seconds of ultrasonic oscillator 18 irradiation 500kHz, and the only particle diameter in the pickle solution is about the SiO of 0.9～2.5 μ m
2Between the particle repeatedly intensely the vibration, ballistic simultaneously the cohesion.In addition, as the SiO that has condensed
2When increasing to certain certain particle diameter, removes on particle with regard to precipitated.The SiO that arrow C 3 expressions of this figure are reclaimed
2Flowing of particle.
Be removed SiO thereafter,
2The pickle solution of particle is sent to steel plate acid-washing device 2 once more, is used for steel plate 1 is carried out pickling.
As shown in Figure 3, the SiO in the pickle solution in the tripping device 6
2It is about 29% that particle is reduced to, and is reduced to approximately 62% in the tripping device 7, is reduced to about 91% in the tripping device 8.Like this, by according to the SiO of containing in the pickle solution
2The mode of the cohesion scope of particle is shone SiO from low frequency to multistage ground, high frequency ground
2Particle from greater particle size among the particle just can condense, precipitate and remove in interim ground effectively to the particle than small particle size.The rate of the removing η that this is shown in Figure 3 is an example, the SiO under each frequency
2The rate of removing of particle is not limited thereto.
And, in the embodiments of the invention 1, though the kind of particulate is SiO
2Particle, but also go for other particulate also can be considered particle size distribution range, suitably the frequency that sets of change or the quantity of ultrasonic oscillator.
In addition, not only can also can set to low frequency multistage ground, make it cohesion to the particle of greater particle size interimly, precipitate and remove from particle than small particle size from low frequency to high frequency multistage ground irradiation frequency from high frequency.For example, setpoint frequency f4 in ultrasonic oscillator 10, setpoint frequency f5 in ultrasonic oscillator 14, setpoint frequency f6 in ultrasonic oscillator 18.The cohesion zone of frequency f 4, f5, f6 is for can contain SiO
2The frequency of the particle size region of particle, and be set to f6＜f5＜f4.By setting to low frequency multistage ground from high frequency like this, just can interimly condense effectively, precipitate and remove to the particle of greater particle size from particle than small particle size.
So, according to the present invention, be possess contain silicon steel plate 1 successively the pickling by carrying out steel plate 1 pickling tank 3, make the pickling installation of the pickle solution round-robin circulating path 5 in the pickling tank 3, owing to, under each frequency f 1, f2, f3, make the SiO of different-grain diameter by to a plurality of different frequency f 1 of the irradiation of round-robin pickle solution multistage ground in circulating path 5, the ultrasonic wave of f2, f3
2Particle coacervation, precipitation, the SiO in the pickle solution that when the pickling of various silicon steel sheets, produces
2Particle reduces, and therefore just can operate and prolong the cycle of maintenance for a long time.In addition, owing to can remove SiO with not stopping pickling installation
2Therefore particle just can obtain high efficiency.
In addition, by a plurality of SiO that separate from pickle solution are set on circulating path 5
2The separator tank 9,13,17 of particle is provided with hyperacoustic each ultrasonic oscillator 10,14,18 that sends different frequency f 1, f2, f3 on each separator tank 9,13,17, just can make SiO reliably from pickle solution
2Particle coacervation, precipitation.
In addition, because by on sidewall 9a, the 13a of separator tank 9,13,17,17a, reflector 11,15,19 being set, the distance of integral multiple of half-wavelength that reflector 11,15,19 and ultrasonic oscillator 10,14,18 is configured in the frequency f 1 set by each ultrasonic oscillator 10,14,18, f2, f3 is last, and sidewall 9a, 13a, the 17a of separator tank 9,13,17 are made with low density material, just can prevent ultrasonic wave from seeing through sidewall 9a, the 13a of separator tank 9,13,17,17a and decay, therefore just can carry out SiO expeditiously
2The cohesion of particle, precipitation.
In addition, by the ultrasonic wave that will send from each ultrasonic oscillator 10,14,18 from the upstream side of circulating path 5 downstream side set to high frequency from low frequency interimly, just can be from the particle of greater particle size to interimly condense effectively, precipitate than the particle of small particle size.
In addition, by the ultrasonic wave that will send from each ultrasonic oscillator 10,14,18 from the upstream side of circulating path 5 downstream side, set to low frequency from high frequency interimly, just can interimly condense effectively, precipitate to the particle of greater particle size from particle than small particle size.
In addition, the cohesion zone of the cohesion zone of frequency of ultrasonic f1, the f2 by will being set by each ultrasonic oscillator 10,14,18, f3 or frequency f 4, f5, f6 is according to containing cohesion, sedimentary SiO from pickle solution
2The mode of the particle size region of particle is set, and just can further reduce the particulate that suspends in pickle solution.
In addition, the SiO by having condensed, precipitating
2Particle reclaims from relief outlet 9c, 13c, 17c, just can remove particulate from pickle solution.
[embodiment 2]
Fig. 4 is the stereographic map of the tripping device of embodiments of the invention 2.Arrow B 5 among the figure, B6 represent flowing of pickle solution.
Tripping device 21 shown in Figure 4 is owing to being that the tripping device 6,7,8 that is disposed on the circulating path 5 of pickling installation shown in Figure 1 to record among the embodiment 1 changes the device that is provided with, and the therefore identical symbol or the explanation of mark are omitted.
Tripping device 21 possesses and is used for separating SiO from pickle solution
2The separator tank 22 of particle, be submerged in the pickle solution that stores in separator tank 22 and send frequency f 1 hyperacoustic ultrasonic oscillator 23, send frequency f 2 hyperacoustic ultrasonic oscillator 24, send hyperacoustic ultrasonic oscillator 25 of frequency f 3 and by according to the reflector 26,27,28 that is provided with mode that these ultrasonic oscillators 23,24,25 are faced mutually.Here, frequency f 1, f2, the f3 of each ultrasonic oscillator 23,24,25 are set to f1＜f2＜f3.The distance of this reflector 26,27,28 and ultrasonic oscillator 23,24,25 is retained as the integral multiple by the half-wavelength of each frequency f 1 of each ultrasonic oscillator 23,24,25 settings, f2, f3.In addition, separator tank 22 possesses the influx 29 that is communicated with and flows into to sidewall 22a opening pickle solution with circulating path 5, is communicated with and flows out to sidewall 22b opening the spout 30 of pickle solution with circulating path 5.
On the sidewall 22c of separator tank 22, begin to be provided with ultrasonic oscillator 23,24,25, on sidewall 22d, be provided with reflector 26,27,28 from upstream side.Sidewall 22c, 22d are formed by low density material, for example foamed styrene etc.In addition, separator tank 22 have the bottom that is formed at sidewall 22a～22d rake 22e, be formed at the relief outlet 22f of the bottom of rake 22e.In addition, be provided with division plate 31,32 and grid 33 on the top of rake 22e.
Here, to be made as A by the space that sidewall 22a, ultrasonic oscillator 23, reflector 26 and division plate 31 surround, to be made as B by the space that ultrasonic oscillator 24, reflector 27 and division plate 31,32 surround, will be made as C by the space that ultrasonic oscillator 25, reflector 28, division plate 29 and sidewall 22b surround.In addition, the concrete numerical value of frequency f 1, f2, f3 adopts the numerical value identical with embodiment 1.
So, by forming described formation, steel plate 1 is supplied with to steel plate acid-washing device 2, in pickling tank 3, utilize pickle solution to carry out cleanup acid treatment.Carried out pickle solution cleanup acid treatment after and flowed out the separator tank 22 of inflow separation device 21 to circulating path 5 thereafter.Store pickle solution in separator tank 22 in the A of space, by the frequency several seconds of ultrasonic oscillator 23 irradiation 10kHz by tens of seconds.At this moment, reflector 26 and ultrasonic oscillator 23 are owing to the distance of the integral multiple of the half-wavelength that is configured in the frequency 10kHz that is set by ultrasonic oscillator 23 is last, and sidewall 22c, 22d are made by the foamed styrene of low density material etc., just can prevent that therefore ultrasonic wave from seeing through sidewall 22c, the 22d of separator tank 22 and decay.
In addition, the only particle diameter in the pickle solution is about the SiO of 6.5～16.0 μ m
2Between the particle repeatedly intensely the vibration, ballistic simultaneously the cohesion.The SiO that has condensed
2Particle will precipitate when increasing to certain certain particle diameter.Sedimentary SiO
2Particle has rake 22e because of separator tank 22, and precipitates reposefully towards relief outlet 22f, is removed from relief outlet 22f.The SiO that from relief outlet 22f, discharges
2Particle is sent to not shown particulate retrieving arrangement etc.The SiO that arrow C 4 expressions of this figure are reclaimed
2Flowing of particle.
Then, pickle solution is sent to space B, is arrived tens of seconds by the frequency several seconds of ultrasonic oscillator 24 irradiation 70kHz, and the only particle diameter in the pickle solution is about the SiO of 2.5～6.5 μ m
2Between the particle repeatedly intensely the vibration, ballistic simultaneously the cohesion.In addition, as the SiO that has condensed
2When increasing to certain certain particle diameter, removes on particle with regard to precipitated.
In addition, pickle solution is sent to space C, is arrived tens of seconds by the frequency several seconds of ultrasonic oscillator 25 irradiation 500kHz, and the only particle diameter in the pickle solution is about the SiO of 0.9～2.5 μ m
2Between the particle repeatedly intensely the vibration, ballistic simultaneously the cohesion.In addition, as the SiO that has condensed
2When increasing to certain certain particle diameter, removes on particle with regard to precipitated.
Be removed SiO thereafter,
2The pickle solution of particle is sent to steel plate acid-washing device 2 once more, is used for steel plate 1 is carried out pickling.In addition, like this with the SiO in the pickle solution
2Under the situation that particle is removed, also can obtain result as shown in Figure 3.
And, in embodiments of the invention 2, though the kind of particulate is SiO
2Particle, but also go for other particulate also can be considered particle size distribution range, suitably the frequency that sets of change or the quantity of ultrasonic oscillator.
In addition, not only can also can set to low frequency multistage ground, make it cohesion to the particle of greater particle size interimly, precipitate and remove from particle than small particle size from low frequency to high frequency multistage ground irradiation frequency from high frequency.For example, setpoint frequency f4 in ultrasonic oscillator 10, setpoint frequency f5 in ultrasonic oscillator 14, setpoint frequency f6 in ultrasonic oscillator 18.The cohesion zone of frequency f 4, f5, f6 is for can contain SiO
2The frequency of the particle size region of particle, and be set to f6＜f5＜f4.By setting to low frequency multistage ground from high frequency like this, just can interimly condense effectively, precipitate and remove to the particle of greater particle size from particle than small particle size.
So, also a plurality of tripping devices 21 can be set on circulating path 5, be set at all different frequencies with being located at the frequency of ultrasonic of being sent in the ultrasonic oscillator of going up separately.
So, according to the present invention, be possess contain silicon steel plate 1 successively the pickling by carrying out steel plate 1 pickling tank 3, make the pickling installation of the pickle solution round-robin circulating path 5 in the pickling tank 3, owing to, under each frequency f 1, f2, f3, make the SiO of different-grain diameter by to a plurality of different frequency f 1 of the irradiation of round-robin pickle solution multistage ground in circulating path 5, the ultrasonic wave of f2, f3
2Particle coacervation, precipitation, the SiO in the pickle solution that when the pickling of various silicon steel sheets, produces
2Particle reduces, and therefore just can operate and prolong the cycle of maintenance for a long time.In addition, owing to can remove SiO with not stopping pickling installation
2Therefore particle just can obtain high efficiency.
In addition, from pickle solution, separate SiO by on circulating path 5, being provided with
2The separator tank 22 of particle is provided with hyperacoustic each ultrasonic oscillator 23,24,25 that sends different frequency f 1, f2, f3 on each separator tank 22, just can make SiO reliably from pickle solution
2Particle coacervation, precipitation.
In addition, because by reflector 26,27,28 is set on the sidewall 22d of separator tank 22, the distance of integral multiple of half-wavelength that reflector 26,27,28 and ultrasonic oscillator 23,24,25 is configured in the frequency f 1 set by each ultrasonic oscillator 23,24,25, f2, f3 is last, and the sidewall 22d of separator tank 22 is made with low density material, just can prevent ultrasonic wave from seeing through the sidewall 22d of separator tank 22 and decay, therefore just can carry out SiO expeditiously
2The cohesion of particle, precipitation.
In addition, by the ultrasonic wave that will send from each ultrasonic oscillator 23,24,25 from the upstream side of circulating path 5 downstream side set to high frequency from low frequency interimly, just can be from the particle of greater particle size to interimly condense effectively, precipitate than the particle of small particle size.
In addition, by the ultrasonic wave that will send from each ultrasonic oscillator 23,24,25 from the upstream side of circulating path 5 downstream side set to low frequency from high frequency interimly, just can interimly condense effectively, precipitate to the particle of greater particle size from particle than small particle size.
In addition, the cohesion zone of frequency of ultrasonic f1, f2 by will being set by each ultrasonic oscillator 23,24,25, the cohesion zone of f3 or frequency f 4, f5, f6 is set according to the mode that contains the particle size region of cohesion, sedimentary particulate from pickle solution, just can further reduce the particulate that suspends in pickle solution.
In addition, the SiO by having condensed, precipitating
2Particle reclaims from relief outlet 22f, just can remove particulate from pickle solution.
In addition, also can on the circulating path 5 of embodiment 1 or 2, ultrasonic oscillator 34 be set as shown in Figure 5, to shining ultrasonic wave to B8 round-robin pickle solution from arrow B 7.The SiO that has condensed
2Particle flows to arrow C 5, and the switching because of open and close valve 35 the relief outlet 5a on being formed at circulating path 5 is removed.Like this, by to round-robin pickle solution direct irradiation ultrasonic wave in circulating path 5, just can further reduce the SiO in the pickle solution
2Particle.
[industrial utilize possibility]
Go in pickle, removing SiO2The device of particle composition, particularly ought be applied to The various silicon steel plates that silicone content is different and the special plate that contains more silicon advance in pickle continuously Very effective in the time of in the continuous acid-washing equipment of row pickling processes.
Claims (9)
1. pickling installation, possess steel plate materials successively the pickling by carrying out this steel plate materials pickling tank, make the pickle solution round-robin circulating path in the described pickling tank, it is characterized in that having ultrasonic wave, the particle coagulation that under each frequency, makes different-grain diameter, sedimentary ultrasonic oscillator to a plurality of different frequencies of the irradiation of round-robin pickle solution multistage ground in described circulating path.
2. pickling installation according to claim 1 is characterized in that, the separator tank of separating particles from pickle solution is set on described circulating path, sends the ultrasonic wave of different frequency on described separator tank by described ultrasonic oscillator.
3. pickling installation according to claim 2, it is characterized in that, on the sidewall of described separator tank, reflector is set, the distance of integral multiple of half-wavelength that described reflector and described ultrasonic oscillator is configured in the frequency of being set by described ultrasonic oscillator is last, and the sidewall of described separator tank is made with low density material.
4. according to any described pickling installation in the claim 1 to 3, it is characterized in that described ultrasonic wave is set to high frequency ground from low frequency by from the upstream side of described circulating path side downstream interimly.
5. according to any described pickling installation in the claim 1 to 3, it is characterized in that described ultrasonic wave is set to low frequency ground from high frequency by from the upstream side of described circulating path side downstream interimly.
6. pickling installation according to claim 4 is characterized in that, the cohesion zone of the frequency of being set by described each ultrasonic oscillator is set according to the mode that contains the particle size region of cohesion, sedimentary particulate from pickle solution.
7. pickling installation according to claim 5 is characterized in that, the cohesion zone of the frequency of being set by described each ultrasonic oscillator is set according to the mode that contains the particle size region of cohesion, sedimentary particulate from pickle solution.
8. according to any described pickling installation in the claim 1 to 3, it is characterized in that the described steel plate materials of the described pickling tank by carrying out pickling is the steel plate materials that contains silicon successively, each ultrasonic wave is condensed, the particulate in the sedimentary pickle solution is SiO
2Particle.
9. according to any described pickling installation in the claim 1 to 3, it is characterized in that, cohesion, the particulate that precipitated are reclaimed.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004119749 | 2004-04-15 | ||
| JP2004119749A JP2005298937A (en) | 2004-04-15 | 2004-04-15 | Pickling equipment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1683593A CN1683593A (en) | 2005-10-19 |
| CN100378247C true CN100378247C (en) | 2008-04-02 |
Family
ID=35263084
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200510067320XA Expired - Fee Related CN100378247C (en) | 2004-04-15 | 2005-04-15 | Acid washing device |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2005298937A (en) |
| KR (1) | KR100646145B1 (en) |
| CN (1) | CN100378247C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BRPI0913196B1 (en) * | 2008-05-30 | 2019-04-16 | Nippon Steel & Sumitomo Metal Corporation | Steel Sheet Stripping Method |
| JP4970623B2 (en) * | 2009-12-03 | 2012-07-11 | 新日本製鐵株式会社 | Steel plate pickling method and pickling apparatus |
| CN106400039A (en) * | 2016-05-26 | 2017-02-15 | 江苏兴隆防腐设备有限公司 | Acid pickling device |
| CN107262443B (en) * | 2017-08-14 | 2023-05-02 | 通威太阳能（安徽）有限公司 | Acid liquor recycling device of graphite boat cleaning machine and cleaning machine thereof |
| DE102017123152A1 (en) * | 2017-10-05 | 2019-04-11 | Sms Group Gmbh | Pickling plant with circulation device |
| CN111778512A (en) * | 2020-07-09 | 2020-10-16 | 浙江协和陶瓷有限公司 | Pickling equipment and pickling method for producing steel plate by using same |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63242933A (en) * | 1987-03-30 | 1988-10-07 | Sumitomo Metal Ind Ltd | Removal of silicon component from hydrochloric acid pickling waste liquid of steel material |
| JPH01111890A (en) * | 1987-10-26 | 1989-04-28 | Mitsubishi Heavy Ind Ltd | Steel sheet pickling device utilizing ultrasonic wave |
| JPH03153889A (en) * | 1989-11-13 | 1991-07-01 | Sumitomo Metal Ind Ltd | Descaling method for hot rolled steel strip |
| JPH0578871A (en) * | 1991-09-24 | 1993-03-30 | Mitsubishi Heavy Ind Ltd | Steel strip pickling device |
| JPH05125573A (en) * | 1991-10-31 | 1993-05-21 | Mitsubishi Heavy Ind Ltd | Continuous pickling and rinsing method and device for steel sheet |
| JP2000256886A (en) * | 1999-03-11 | 2000-09-19 | Nippon Steel Corp | Descaling method for hot rolled steel sheet |
-
2004
- 2004-04-15 JP JP2004119749A patent/JP2005298937A/en active Pending
-
2005
- 2005-04-07 KR KR1020050028809A patent/KR100646145B1/en active IP Right Grant
- 2005-04-15 CN CNB200510067320XA patent/CN100378247C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63242933A (en) * | 1987-03-30 | 1988-10-07 | Sumitomo Metal Ind Ltd | Removal of silicon component from hydrochloric acid pickling waste liquid of steel material |
| JPH01111890A (en) * | 1987-10-26 | 1989-04-28 | Mitsubishi Heavy Ind Ltd | Steel sheet pickling device utilizing ultrasonic wave |
| JPH03153889A (en) * | 1989-11-13 | 1991-07-01 | Sumitomo Metal Ind Ltd | Descaling method for hot rolled steel strip |
| JPH0578871A (en) * | 1991-09-24 | 1993-03-30 | Mitsubishi Heavy Ind Ltd | Steel strip pickling device |
| JPH05125573A (en) * | 1991-10-31 | 1993-05-21 | Mitsubishi Heavy Ind Ltd | Continuous pickling and rinsing method and device for steel sheet |
| JP2000256886A (en) * | 1999-03-11 | 2000-09-19 | Nippon Steel Corp | Descaling method for hot rolled steel sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005298937A (en) | 2005-10-27 |
| KR20060045550A (en) | 2006-05-17 |
| KR100646145B1 (en) | 2006-11-14 |
| CN1683593A (en) | 2005-10-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100378247C (en) | Acid washing device | |
| Donaldson et al. | Lifting the scales from our pipes | |
| US1831075A (en) | Means of removing scale matter from liquids | |
| CN106902976A (en) | A kind of slurry magnetic separator | |
| EP0040369A1 (en) | Apparatus for the surface treatment of an object | |
| CN108996713A (en) | A kind of vibration apparatus for eliminating sludge and system, vibration scale removal control system and vibration descaling method | |
| CN116497299A (en) | Salt bath isothermal quenching heat treatment process method for diamond wire brass wire | |
| CN208163416U (en) | A kind of water circle device and the vertical mill with the water circle device | |
| JPH06277655A (en) | Concentration of solution and seawater desalting system | |
| CN209548778U (en) | Horizontal sedimentation tank and horizontal sedimentation tank system | |
| CN102605114A (en) | Slag flushing process and system for ironmaking | |
| JP7250300B2 (en) | Heat exchange equipment with scale countermeasures | |
| CN208648852U (en) | In a kind of waste acid water filter tank and device | |
| JPS60155889A (en) | Method and device for treating slag | |
| CN209024282U (en) | A kind of vibration apparatus for eliminating sludge and system, vibration scale removal control system | |
| JP6939498B2 (en) | Fluid roasting furnace | |
| CN109529411A (en) | Horizontal sedimentation tank and horizontal sedimentation tank system | |
| JP3053755B2 (en) | Treatment method of pickling solution for metal materials | |
| CN107235597A (en) | A kind of nonhomogen-ous nucleation crystallisation handles the method and system of desulfurization wastewater | |
| US3278027A (en) | Grit reclamation method | |
| US20030079759A1 (en) | Apparatus for cleaning glass substrate for use in information recording medium | |
| CN204778868U (en) | Aluminium oxide high pressure dissolves out dilution trap exhaust steam recovery unit | |
| JP2012024721A (en) | Method for recovering scale, and heat treatment furnace of steel using the same | |
| JPH0460720B2 (en) | ||
| CN109626687A (en) | A kind of mine water based on ultrasound freezing desalting system and method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20151030 Address after: Japan Tokyo port, 34 No. 6 Chicago Patentee after: PRIMETALS TECHNOLOGIES JAPAN, Ltd. Address before: Tokyo, Japan Patentee before: MITSUBISHI-HITACHI METALS MACHINERY, Inc. |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080402 |