CN1485287A - System and method for removing organic oxide from waste water - Google Patents
System and method for removing organic oxide from waste water Download PDFInfo
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- CN1485287A CN1485287A CNA02143090XA CN02143090A CN1485287A CN 1485287 A CN1485287 A CN 1485287A CN A02143090X A CNA02143090X A CN A02143090XA CN 02143090 A CN02143090 A CN 02143090A CN 1485287 A CN1485287 A CN 1485287A
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Abstract
A flow of removing organic compounds through oxidation by introducing ozone and ultraviolet radiation, which belongs to removing organic compounds through oxidation from waste water discharged by semiconductor, LCD and other industrials. The system comprises ultraviolet rays/ozone oxidation removal module, or one or several removal modules in series, the series could be continuous or discontinuous. One ultraviolet rays/ozone oxidation removal module mainly includes ozone generator, ozone inhaler, ozone dissolution vessel, ozone destroying device, UV reactive vessel and reflowing circuit. The efficiency of ultraviolet rays/ozone oxidation removal module is controlled by the reflowing water ratio, ozone concentration, intensity of ultraviolet rays.
Description
Technical field
The invention relates to semi-conductor, liquid-crystal display related industries processing procedure waste discharges such as (LCD), even the organic oxidation removal of the waste water that contains organic pollutant that other cause produced, be by injecting ozone and removing flow process and device about a kind of through the waste water oxidation operation of UV-irradiation.
Background technology
The Taiwan is because special geographical environment, the water storage deficiency, Water resources development is difficult for, and the water consumption of various industries increases year by year, especially along with the expansion of semi-conductor production capacity, water requirement multiple is especially grown up, and makes the interior manufacturer of science park of Taiwan face serious lack of water and restriction water pressure, add that the new water resources development of exploitation is difficult for, make the water resources imbalance become obvious problem.The ratio that present Hsinchu science park has required newly-built semiconductor factory processing procedure discharge water to be recycled to ultrapure water system and other secondary water need reach more than 85%, and old factory also needs more than 70%, the platform south science park in the exploitation then in the regulation garden the full station-service water rate of recovery of semiconductor factory need reach more than 85%.So the theory that promotes the recovery of processing procedure water and utilize is the direction of current very urgent effort.
The manufacture of semiconductor waste discharge be one of pointer of recovery with total organic matter (be called for short TOC), major cause be influence semi-conductor and LCD process rate micropollution more than 90% from organic substance.Organic substance such as Virahol in the processing procedure waste discharge (being called for short IPA), N-methyl tetrahydro pyrrolidine ketone (being called for short NMP) etc.Be lower than waste water that TOC reclaims limit value and just can selectedly deliver to the organic matter removal system or do not handle and reclaim, otherwise, then be discharged.At present, the TOC of real factory reclaims limit value and is about 0.5～5ppm, is lower than 70% problem but face the rate of recovery.In order to promote the rate of recovery, the proposition of real factory improves TOC and reclaims limit value, increases the wastewater flow rate that enters the organic matter removal system, to promote the policy of improving more than the rate of recovery to 70%.But, reclaim limit value if improve TOC, just organic matter removal technology that present real factory adopts such as activated carbon adsorption, reverse osmosis are filtered, biological bed filters and can lose its function because of the limit of its technology.Because aforementioned techniques generally can only be handled the waste water of TOC concentration in 0.5～5ppm scope, because the water quality variation was too big after the competitive adsorption of activated carbon and desorption reaction caused and handle, the low problem that reaches and bacteria breed is arranged of clearance of TOC is filtered in reverse osmosis, and biological bed filtration causes biology bed afunction greatly because of the change of water quality fluctuation, the treatment process that the original bottleneck of above-mentioned script need be broken through is felt simply helpless especially for the waste water of higher organic content, so that can't reach the requirement that improves the processing procedure rate of recovery, so water supply is critical, the water resources development difficulty, but founding the factory in a large number and need the industry of a large amount of waters for reaching the economic production scale, is a big strike.In addition, the advanced oxidation processes of UV/Ozone successfully is effectively applied to organic removal for a long time, and it can be CO with the organic substance complete oxidation
2, be different from the mode of physical treatment such as activated carbon adsorption, certain some that only organic substance is isolated in system is filtered in reverse osmosis, causes the ultrapure water system that contaminated potential crisis is arranged again; And also suitable the stablizing of its usefulness, far above the treatment process of biology.UV/Ozone effectively is successfully applied to semi-conductor and the LCD processing procedure waste water of removing high-enriched organics so far as yet, and therefore, this is the motivation that we attempt developing this system.
Summary of the invention
Main purpose of the present invention is to propose a cover and utilizes ozone to inject waste water again through ultraviolet radiation the oxidation removal flow process and the device of (being called for short UV/ozone), to handle semi-conductor and LCD processing procedure discharging TOC waste water.
Organic oxidation removal module in a kind of waste water of the present invention comprises:
One ozone inhaler, it is suitable for connecting respectively one and is used to pump into the motor of desiring processed water, reaches an ozone generation device, and this ozone inhaler is used to mix this desire processed water and ozone source gas;
One ozone solution groove, it receives ozone/waste water mixed solution that this ozone inhaler produces, and provides organism in ozone and this desire processed water to carry out a residence time of oxidizing reaction;
One ultraviolet reactive tank, it receives the waste water ozoniferous from this ozone solution groove, and makes this waste water ozoniferous through UV-irradiation, makes organism wherein carry out photochemical oxidation;
One additional purification assembly optionally, this additional purification assembly are film processing components, ion-exchange assembly, activated carbon adsorption assembly or degassing assembly, are used for that ultraviolet reactive tank is gone out flowing water and are further purified; And
One backflow mechanism, comprise and be used for this ultraviolet ray reactive tank gone out that flowing water maybe is back to the pipeline of this desire processed water with the some that goes out flowing water of this additional purification assembly when this additional purification assembly exists and the return line that constitutes some wherein, outflow tube road treatment stage that another partly being gone out flowing water and goes out to flow to next, and one or more valves are used to control the flow proportional that go out flowing water of recirculation water to next treatment stage.
Preferable, this backflow mechanism comprises a flowrate control valve that is positioned on this outflow tube road, be positioned at another flowrate control valve on this return line, and one is located at pipeline that this return line enters this desires processed water being used to before and prevents that this desire processed water from entering the reverse checkvalve of this return line.
Preferable, module of the present invention further comprises a constant pressure valve that is connected in this ozone solution groove top, one gas-liquid separator and be connected in an ozone breaker of this gas-liquid separator, wherein the constant pressure valve at this ozone solution groove top is fixed in some pressure with the ozone in the ozone solution groove/waste water mixed solution, and can make greater than the ozone that sets pressure and be expelled to this gas-liquid separator, this gas-liquid separator is used to separate aqueous vapor, avoids water to enter this ozone breaker.
The present invention also proposes oxidation operation removal system in a kind of waste water, comprise a plurality of continuously placed in-line aforementioned modules of the present invention or further comprise the additional purification assembly of the one or more polyphones in two adjacent modules wherein, this additional purification assembly is film processing components, ion-exchange assembly, activated carbon adsorption assembly or degassing assembly, and it is used for further handling going out flowing water previous stage.
The present invention also proposes organic oxidation removal method in a kind of waste water simultaneously, comprises the following steps:
A) desire processed water with one and mix, and form the mixed solution of ozone concn between 3-100ppm with ozone source gas;
B) ozone/waste water mixed solution that step a) produced is imported an ozone solution groove, and in wherein carrying out ozone solution and oxidizing reaction one between the 10-150 residence time of second;
C) make the effusive ozonize of this ozone solution groove cross water and flow through a ultraviolet reactive tank, and in wherein being subjected to UV-irradiation, the organism that ozonize is crossed in the water carries out photochemical oxidation; And
D) some that will cross water from the effusive UV-irradiation of this ultraviolet ray reactive tank as go out flowing water and be expelled to next the treatment stage and another partly reflux as the some of the desire processed water of step a), wherein this recirculation water and the flow proportional that goes out flowing water are between 0.5: 1-20: 1.
Relevant preceding case that following tabular applicant investigates and function, means and the difference on effect of inventing with this case:
| US?Pat. No. | Time | The inventor | The patent application explanation | Explanation with this case difference |
| 4,792,407 4,849,114 | 1988 1989 | Zeff?et?al. | In conjunction with ozone, UV and H 2O 2Processing comprises methylene chloride, methanol and the halogen-containing class material in underground water, trade effluent, the tap water | H is not added in this case 2O 2Only utilize UV/ozone to handle, and it is different to handle organic substance at semi-conductor and LCD processing procedure waste discharge |
| 4,863,608 5,302,356 5,395,522 5,868,924 6,030,526 | 1989 1994 1995 1999 2000 | Kawai?et?al. Shadman?et al. Melanson?et al. Nachtman?et al. Porter | Remove micro-TOC in the water or be a processing unit in the ultrapure water treatment facility, treatment scheme is mainly light-catalyzed reaction, utilizes TiO 2，SrTiO 3Or Pt, Pd, Ru, RuO 2Reach the coating of materials such as Rh and carry out the degraded of organic substance through the UV light irradiation | This case utilizes semi-conductor and the LCD processing procedure waste discharge of UV/ozone routine processes object for left higher TOC concentration of listed concentration; And it is different that flow process and dress are shaped on institute |
| 4,990,260 | 1991 | Pisani | Utilize cavitation device and UV reactor for treatment to make the industry cleaning link water, water quality treatment is down to TOC content 10ppb from the scope of 18M Ω-cm, solubilised state inoganic solids thing 1ppt and TOC content 100ppb | This case utilizes the UV/ozone routine processes |
| 5,573,662 | 1996 | Abe?et?al. | (TOC:0.5～3ppm) handle extremely＜1ppb, treatment scheme comprises that RO, vacuum gas are carried, low pressure UV reactor reaches and mixes bed to reclaim low TOC waste water | This case utilizes the UV/ozone routine processes |
Description of drawings
Fig. 1 shows the block flow diagram of organic oxidation removal module 13 in a kind of waste water of finishing according to a preferred embodiment of the present invention.
Fig. 2 shows the block flow diagram of organic oxidation removal module 15 in a kind of waste water of finishing according to another preferred embodiment of the present invention.
Fig. 3 shows the block flow diagram of the system 17 of N UV/ozone oxidation removal module of series connection of the present invention, and wherein UV/ozone oxidation removal module is the module 13 among Fig. 1.
Fig. 4 shows the block flow diagram of the system 18 of the individual UV/ozone oxidation removal of series connection of the present invention (N+M) module, wherein inserts an additional purifying assembly 14.
Fig. 5 shows the block flow diagram of several discontinuous UV/ozone oxidation removal modular systems 19 of the present invention, and wherein two 13 of adjacent modules are inserted with an additional purifying assembly 14.
The figure number explanation of primary clustering
1. motor 2. ozone inhaler 3. ozone generation devices
4. ozone solution groove 5. constant pressure valves 6. gas-liquid separators
7. ozone breaker 8. ultraviolet reactive tank 9,12. flowrate control valves
11. reverse checkvalve 10. return lines 14. additional purification assemblies
Oxidation operation is removed module 16. aqua storage tanks in 13,15. waste water
Oxidation operation is removed system in 17,18,19. waste water
Detailed description of the invention
Organic oxidation removal module 13 is shown in Fig. 1 in a kind of waste water of finishing according to a preferred embodiment of the present invention, wherein motor 1 with the processed water pressurized delivered to ozone inhaler 2, ozone inhaler 2 can suck gas mixes with current, this device material is the material of anti-ozone corrosion, in this adjustment via motor 1 and a flow control valve door 9, can suck the ozone gas of different flow. Ozone gas is by ozone generation device 3 outputs and provide to ozone inhaler 2. The ozone of this ozone inhaler 2 is mixed ozone and waste water/waste water mixed liquor then enters an ozone dissolved groove 4, and it provides time and the space of gas contact, and ozone dissolved groove 4 is made for the 316L stainless steel, or the material of other anti-ozone corrosion. One tool constant pressure valve 5 is fixed in some pressure with the ozone dissolved groove, and can make greater than the ozone that sets pressure and be expelled to gas-liquid separator 6, is connected to ozone breaker 7 again. Gas-liquid separator 6 separable aqueous vapors avoid water to enter ozone breaker 7. The purpose of ozone breaker 7 is with the ozone layer destroying in the Exhaust Gas. Waste water enters ultraviolet ray (UV) reactive tank 8 and carries out the ultraviolet radiation oxidation reaction after ozone dissolved groove 4 flows out, UV fluorescent tube in the cell body can carry out to the water of the cell body of flowing through the photochemical oxidation reaction, used herein is medium pressure mercury lamp, and also can use low pressure or high-pressure sodium lamp on the implementation. This flow control valve 9 is located at ultraviolet reactive tank 8 outlets, can control thus the back outlet pressure of ozone inhaler 2. One return line 10, be connected on this flow control valve 9 after, mix with untreated waste water before the water sample some sent back to motor 1 again after it will be processed, thus with the TOC concentration in the dilution water, and the time of staying of increase waste water; Return line flow to motor 1 front installation one non-return valve 11 and avoids untreated waste water to flow in the return line. Another flow control valve 12 is located on the return line 10, can control thus to reflux and go out the stream ratio, and the reflux ratio of native system (reflux ratio=backflow water yield: go out streamflow) is controlled in 0.5: 1～between 20: 1.
Fig. 2 is the change application mode 15 that other purifying assembly 14 is installed in the oxidation removal module 13. The flowing water that goes out behind this flow control valve 9 enters other purifying assembly 14 again, such as film processing components, ion-exchange assembly, active carbon adsorption assembly, degassed assembly etc., can with in the water or the ionic species that produces of oxidation reaction, particulate matter or the supersaturated gas that produces because of course of dissolution remove.
Fig. 3 is the system 17 of N UV/ozone oxidation removal module of series connection, and wherein UV/ozone oxidation removal module is the module 13 among Fig. 1. Aqua storage tank 16 is for collecting processing procedure discharging organic wastewater. When processing procedure discharging organic wastewater enters to first UV/ozone oxidation removal module 13 by aqua storage tank 16, dissolved ozone concentration and backflow ratio are controlled in above-mentioned optimal performance condition, carried out oxidation reaction to reduce TOC concentration, enter again afterwards second UV/ozone oxidation removal module 13 and carry out the oxidation removal reaction, same operation repeats N time, and the TOC oxidation removal that processing procedure discharges in the organic wastewater is processed to TOC concentration qualified or expection. N is positive integer.
Fig. 4 is the system 18 of several UV/ozone oxidation removal modules of discontinuous series winding. The organic waste discharge of processing procedure enters M UV/ozone oxidation removal module 13 by aqua storage tank 16, control dissolved ozone concentration and backflow ratio are in above-mentioned optimal performance condition, carry out the oxidation removal reaction, reduce TOC concentration, pass through again other purifying assembly 14 of several identical or different, non-UV/ozone oxidation removal modules, such as film processing components, active carbon adsorption assembly, ion-exchange assembly, degassed assemblies etc., N the UV/ozone oxidation removal module 13 of flowing through again processes the TOC oxidation removal that processing procedure discharges in the organic wastewater to the TOC concentration of qualified or expection. M and N are positive integer.
Fig. 5 is several discontinuous UV/ozone oxidation removal modular systems 19. The organic waste discharge of processing procedure enters a UV/ozone oxidation removal module 13 by aqua storage tank 16, pass through again other purifying assembly 14 of other non-UV/ozone oxidation removal module, such as film processing components, active carbon adsorption assembly, ion-exchange assembly, degassed assembly etc., enter again a UV/ozone oxidation removal module 13, said procedure repeats N time, and the TOC oxidation removal that processing procedure discharges in the organic wastewater is processed to TOC concentration qualified or expection. N is positive integer.
Embodiment
Embodiment 1:
Use module as shown in Figure 1 to a waste water that contains about 18600 ppb of TOC value of IPA, carry out oxidation operation and remove experiment.
The ozone concn of the ozone/waste water mixed solution in the ozone inhaler maintains 20ppm, and pressure difference is 2.8kg/cm
2The ozone solution groove residence time is 41 seconds.Recirculation water was controlled in 4: 1 with the flow proportional that goes out flowing water.Go out flowing water TOC value and reduce to 12250ppb, clearance is 34%.Repeat to implement above-mentioned experimental procedure, the TOC value is reduced to 7840ppb from 12250ppb, and clearance is 36%.Repeat to implement above-mentioned experimental procedure again, the TOC value is reduced to 4468ppb from 7840ppb, and clearance is 43%.Hence one can see that, and when implementing above-mentioned steps again and again, this waste water can be reduced to desired concentration range; And the series connection of implementing UV/ozone oxidation removal module can be continuous or discontinuous, promptly inserts other purifying assembly of other non-UV/ozone oxidation removal module at a module and next intermodule.
Embodiment 2:
Repeat the experimental procedure of embodiment 1, but influent stream water changes a waste water that contains the about 10053ppb of TOC value of NMP into, goes out flowing water TOC value and is about 6700ppb, clearance is 33%.Repeat to implement above-mentioned experimental procedure, the TOC value is reduced to about 3820ppb from 6700ppb, and clearance is 43%.Hence one can see that, and when implementing above-mentioned steps again and again, this waste water can be reduced to desired concentration range; And the series connection of implementing UV/ozone oxidation removal module can be continuous or discontinuous, promptly inserts other purifying assembly of other non-UV/ozone oxidation removal module at a module and next intermodule.
Claims (7)
1. organic oxidation removal module in the waste water comprises:
One ozone inhaler, it is suitable for connecting respectively one and is used to pump into the motor of desiring processed water, reaches an ozone generation device, and this ozone inhaler is used to mix this desire processed water and ozone source gas;
One ozone solution groove, it receives ozone/waste water mixed solution that this ozone inhaler produces, and provides organism in ozone and this desire processed water to carry out a residence time of oxidizing reaction;
One ultraviolet reactive tank, it receives the waste water ozoniferous from this ozone solution groove, and makes this waste water ozoniferous through UV-irradiation, makes organism wherein carry out photochemical oxidation;
One additional purification assembly optionally, this additional purification assembly are film processing components, ion-exchange assembly, activated carbon adsorption assembly or degassing assembly, are used for that ultraviolet reactive tank is gone out flowing water and are further purified; And
One backflow mechanism, comprise and be used for this ultraviolet ray reactive tank gone out that flowing water maybe is back to the pipeline of this desire processed water with the some that goes out flowing water of this additional purification assembly when this additional purification assembly exists and the return line that constitutes some wherein, outflow tube road treatment stage that another partly being gone out flowing water and goes out to flow to next, and one or more valve is used to control the flow proportional that go out flowing water of recirculation water to next treatment stage.
2. module as claimed in claim 1, wherein should backflow mechanism comprise a flowrate control valve that is positioned on this outflow tube road, be positioned at another flowrate control valve on this return line, and one is located at pipeline that this return line enters this desires processed water being used to before and prevents that this desire processed water from entering the reverse checkvalve of this return line.
3. module as claimed in claim 1, it further comprises a constant pressure valve that is connected in this ozone solution groove top, one gas-liquid separator and be connected in an ozone breaker of this gas-liquid separator, wherein the constant pressure valve at this ozone solution groove top is fixed in some pressure with the ozone in the ozone solution groove/waste water mixed solution, and can make greater than the ozone that sets pressure and be expelled to this gas-liquid separator, this gas-liquid separator is used to separate aqueous vapor, avoids water to enter this ozone breaker.
4. oxidation operation is removed system in the waste water, comprise a plurality of continuously placed in-line modules as claimed in claim 1 or further comprise the additional purification assembly of the one or more polyphones in two adjacent modules wherein, this additional purification assembly is film processing components, ion-exchange assembly, activated carbon adsorption assembly or degassing assembly, and it is used for being further purified going out flowing water previous stage.
5. oxidation operation is removed system in the waste water, comprise a plurality of continuously placed in-line modules as claimed in claim 2 or further comprise the additional purification assembly of the one or more polyphones in two adjacent modules wherein, this additional purification assembly is film processing components, ion-exchange assembly, activated carbon adsorption assembly or degassing assembly, and it is used for being further purified going out flowing water previous stage.
6. oxidation operation is removed system in the waste water, comprise a plurality of continuously placed in-line modules as claimed in claim 3 or further comprise the additional purification assembly of the one or more polyphones in two adjacent modules wherein, this additional purification assembly is film processing components, ion-exchange assembly, activated carbon adsorption assembly or degassing assembly, and it is used for being further purified going out flowing water previous stage.
7. organic oxidation removal method in the waste water comprises the following steps:
A) desire processed water with one and mix, and form the mixed solution of ozone concn between 3-100ppm with ozone source gas;
B) ozone/waste water mixed solution that step a) produced is imported an ozone solution groove, and in wherein carrying out ozone solution and oxidizing reaction one between the 10-150 residence time of second;
C) make the effusive ozonize of this ozone solution groove cross water and flow through a ultraviolet reactive tank, and in wherein being subjected to UV-irradiation, the organism that ozonize is crossed in the water carries out photochemical oxidation; And
D) some that will cross water from the effusive UV-irradiation of this ultraviolet ray reactive tank as go out flowing water and be expelled to next the treatment stage and another partly reflux as the some of the desire processed water of step a), wherein this recirculation water and the flow proportional that goes out flowing water are between 0.5: 1-20: 1.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB02143090XA CN1231421C (en) | 2002-09-28 | 2002-09-28 | System and method for removing organic oxide from waste water |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB02143090XA CN1231421C (en) | 2002-09-28 | 2002-09-28 | System and method for removing organic oxide from waste water |
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| CN1231421C CN1231421C (en) | 2005-12-14 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304307C (en) * | 2005-10-09 | 2007-03-14 | 天津工业大学 | Dyeing waste-water decolorizing degradation, recovery and utilization |
| CN100357393C (en) * | 2005-11-25 | 2007-12-26 | 清华大学 | Liquid crystal purifying method |
| CN102198997A (en) * | 2011-04-15 | 2011-09-28 | 四川省环保科技工程有限责任公司 | Treatment process method for wastewater from abscisic acid production |
| CN107572739A (en) * | 2017-11-12 | 2018-01-12 | 济宁市山化环保科技有限公司 | A kind of method for being used to prevent that Organic substance in water from contacting with water |
| CN107935267A (en) * | 2017-12-14 | 2018-04-20 | 浙江启尔机电技术有限公司 | There is the ultrapure water preparation device of adjusting water outlet total organic carbon for liquid immersion lithography |
| CN108083418A (en) * | 2017-12-28 | 2018-05-29 | 大连东泰产业废弃物处理有限公司 | A kind of system and method using ozone treatment waste water |
| CN117559026A (en) * | 2024-01-11 | 2024-02-13 | 广东杰成新能源材料科技有限公司 | Battery material decomposition device and waste battery recycling system |
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2002
- 2002-09-28 CN CNB02143090XA patent/CN1231421C/en not_active Expired - Lifetime
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304307C (en) * | 2005-10-09 | 2007-03-14 | 天津工业大学 | Dyeing waste-water decolorizing degradation, recovery and utilization |
| CN100357393C (en) * | 2005-11-25 | 2007-12-26 | 清华大学 | Liquid crystal purifying method |
| CN102198997A (en) * | 2011-04-15 | 2011-09-28 | 四川省环保科技工程有限责任公司 | Treatment process method for wastewater from abscisic acid production |
| CN102198997B (en) * | 2011-04-15 | 2012-10-10 | 四川省环保科技工程有限责任公司 | Treatment process method for wastewater from abscisic acid production |
| CN107572739A (en) * | 2017-11-12 | 2018-01-12 | 济宁市山化环保科技有限公司 | A kind of method for being used to prevent that Organic substance in water from contacting with water |
| CN107935267A (en) * | 2017-12-14 | 2018-04-20 | 浙江启尔机电技术有限公司 | There is the ultrapure water preparation device of adjusting water outlet total organic carbon for liquid immersion lithography |
| CN107935267B (en) * | 2017-12-14 | 2023-12-12 | 浙江启尔机电技术有限公司 | Ultrapure water preparation device with total organic carbon of effluent adjustment for immersion lithography |
| CN108083418A (en) * | 2017-12-28 | 2018-05-29 | 大连东泰产业废弃物处理有限公司 | A kind of system and method using ozone treatment waste water |
| CN117559026A (en) * | 2024-01-11 | 2024-02-13 | 广东杰成新能源材料科技有限公司 | Battery material decomposition device and waste battery recycling system |
| CN117559026B (en) * | 2024-01-11 | 2024-03-29 | 广东杰成新能源材料科技有限公司 | Battery material decomposition device and waste battery recycling system |
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| Publication number | Publication date |
|---|---|
| CN1231421C (en) | 2005-12-14 |
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