CN106064826A - A kind of method and apparatus utilizing wiring board acidic etching waste liquid to reclaim copper resource - Google Patents
A kind of method and apparatus utilizing wiring board acidic etching waste liquid to reclaim copper resource Download PDFInfo
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- CN106064826A CN106064826A CN201610384908.6A CN201610384908A CN106064826A CN 106064826 A CN106064826 A CN 106064826A CN 201610384908 A CN201610384908 A CN 201610384908A CN 106064826 A CN106064826 A CN 106064826A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/04—Halides
- C01G3/05—Chlorides
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract
The present invention relates to acidic etching waste liquid recovery technology field, particularly relate to a kind of method and apparatus utilizing wiring board acidic etching waste liquid to reclaim copper resource, described method is with wiring board cupric acidic etching waste liquid as raw material, sodium carbonate slip is joined under room temperature and stirring condition, it is settled out crude product curpic carbonate, filter after separating crude product curpic carbonate, after water fully washs, add hydrochloric acid transfer copper chloride to, anhydrous cupric chloride is directly prepared with spray drying method, or distillation and concentration, crystallize out copper chloride dihydrate product, there is the response rate high, resource makes full use of, environmental protection is friendly, non-secondary pollution, technique is simple, condition is easily controlled, the simple advantage of equipment.
Description
Technical field
The present invention relates to acidic etching waste liquid recovery technology field, particularly relate to one and utilize wiring board acid etching to give up
Liquid reclaims the method and apparatus of copper resource.
Background technology
Modern science and technology develops rapidly, and circuit board etching industry also develops rapidly, and the contained waste liquid that etching industry is discharged is also with increasing
Add.Someone adds up, and whole world year discharge waste liquid China accounts for four point about one, and along with nation-building develops further, this copper resource is anxious
More economical and green formula ground is needed to recycle.To this end, forefathers have made substantial amounts of research, and write effect, such as Chinese patent
CN105016373.A, CN103241762, CN104925847A, CN105236465A, CN101691240B,
200710074010.X, 201410337012.3 and 201510815459.1 etc..
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, and provide one to utilize wiring board acidic etching waste liquid to return
The method and apparatus receiving copper resource, the response rate is high, and resource makes full use of, and environmental protection is friendly, non-secondary pollution, and technique is simple, condition
Being easily controlled, equipment is simple.
For achieving the above object, the present invention adopts the following technical scheme that.
A kind of method utilizing wiring board acidic etching waste liquid to reclaim copper resource, it is with wiring board cupric acidic etching waste liquid
For raw material, under room temperature and stirring condition, join sodium carbonate slip, be settled out crude product curpic carbonate, filter and separate crude product curpic carbonate
After, after water fully wash, add hydrochloric acid transfer copper chloride to, directly prepare anhydrous cupric chloride, or distillation and concentration with spray drying method,
Crystallize out copper chloride dihydrate product；Particularly as follows:
Step one, prepares sodium carbonate slip: under room temperature and stirring condition, in retort, adds required aqueous sodium carbonate
Later filtrate, makes sodium carbonate slip；
Step 2, is settled out crude product curpic carbonate: under agitation, at ambient temperature that the desired amount of wiring board cupric is acid
Etching waste liquor is slowly added to or in porous distributor pipe flows into sodium carbonate slip, forms crude product curpic carbonate precipitation, terminal point control
PH6-8, after adding, is stirred for；
Step 3, filters and separates crude product curpic carbonate: the crude product curpic carbonate that will make, and considers liquid with thick by filtration system isolated
Product curpic carbonate；
Step 4, wet product curpic carbonate washs: crude product curpic carbonate, through water wash system, obtains wet product curpic carbonate, in its wet product curpic carbonate
Sodium content is less than 0.1%；
Step 5, wet product curpic carbonate adds hydrochloric acid and is converted into copper chloride: the wet product curpic carbonate after scrubbed adds concentrated hydrochloric acid, stirs molten
Copper chloride solution is obtained after solution, its acidity PH1-2, filters and separates a small amount of insoluble matter, keep a small amount of acidity, desirably prevent chlorination
The hydrolysis of copper；
Step 6, prepares copper chloride product: method one, prepares anhydrous chlorine containing refined copper chloride solution by spray drying device
Change copper；Method two, containing refined copper chloride solution by distillation and concentration, under 26-42 degree Celsius, crystallisation by cooling, then passed through
Filter system prepares copper chloride dihydrate product.
Preferably, the sodium carbonate slip used is the one in sodium carbonate potassium carbonate sodium bicarbonate or its mixture.
Preferably, crude product curpic carbonate is only stirred at room temperature washing with water, washes sodium in rear wet product curpic carbonate and can reach management and control and want
Ask.
Preferably, adding concentrated hydrochloric acid, change into fine copper chloride product after the washing of described crude product curpic carbonate, its purity reaches
More than 98.0%.
Preferably, the worry liquid obtained in step 3, a part is back to crude product carbonic acid processed as later filtrate by slurrying
Copper, a part of by preparation oxidant reuse circuit board etching line.
A kind of equipment utilizing wiring board acidic etching waste liquid to reclaim copper resource, it includes the crude product set gradually by station
Curpic carbonate preparation facilities, crude product curpic carbonate wash mill and copper chloride product preparation facilities；
Described crude product curpic carbonate preparation facilities include reactor, slush pump A, agitator tank A, filtration system A, residue collection groove A and
Considering liquid collecting tank A, described slush pump A to be connected between reactor and agitator tank A, agitator tank A connects filter system A, and filter system A is even
Meet residue collection groove A and consider liquid collecting tank A；Described reactor is provided with porous distributor pipe；
Described crude product curpic carbonate wash mill includes agitator tank B1, slurry pump B, agitator tank B2, filtration system B, residue collection groove B
With worry liquid collecting tank B, described slurry pump B connects between agitator tank B1 and agitator tank B2, and agitator tank B2 connects filter system B, filter system
System B connects residue collection groove B and considers liquid collecting tank B；
Described copper chloride product preparation facilities is copper chloride solution anhydrous cupric chloride device or copper chloride solution system two water chlorination
Copper device；
Described copper chloride solution anhydrous cupric chloride device includes that reactor C, kinetic pump C1, fine filtering apparatus C, copper chloride liquid store up
Tank C, kinetic pump C2, heat blower, spray dryer, anhydrous cupric chloride packing device, described kinetic pump C1 is connected to reaction
Between still C and fine filtering apparatus C, fine filtering apparatus C connects copper chloride liquid storage tank C, kinetic pump C2 and is connected to copper chloride liquid storage tank C
With between spray dryer, heat blower connects spray dryer, spray dryer connects anhydrous cupric chloride packing device；
Described copper chloride solution copper chloride dihydrate device include reactor D, kinetic pump D, fine filtering apparatus D, distillation and concentration device,
Filtration system D, copper chloride dihydrate packing device, described kinetic pump D is connected between reactor D and fine filtering apparatus D, filters dress
Putting D and connect distillation and concentration device, distillation and concentration device connects filtration system D, and filtration system D connects copper chloride dihydrate packing device.
Preferably, described agitator tank A, agitator tank B1, the mixing apparatus of slurry pump B can be mechanical agitation, bubbling stirring
Or the one in vibrations mixing apparatus.
Preferably, institute's filtration system B can be vacuum filter, pressure filter, centrifuge, and filter medium can be sand core filter
Plate, ceramic filtering plate, filter cloth or Organic substance height filter press plate, centrifuge can be Horizontal helical type centrifuge, flat or 3-foot is automatic
Conveyer centrifugal.
Present invention have the beneficial effect that a kind of method utilizing wiring board acidic etching waste liquid to reclaim copper resource of the present invention
And equipment, wiring board acidic etching waste liquid copper resource is all reclaimed with crude product curpic carbonate form, the response rate 99.9%, resource is filled
Dividing and utilize, environmental protection is friendly, non-secondary pollution, and technique is simple, and condition is easily controlled, and equipment is simple, all can supply from domestic market,
Reduced investment, low cost, remarkable in economical benefits, can be processed into multiple copper fine product with crude product curpic carbonate, such as copper chloride copper sulfate
Basic copper carbonate copper oxides etc., as a example by being processed into copper chloride, just estimate often 1 ton of copper of recovery and can increase profit 2.4 ten thousand yuan, compare membrane electrolysis
High financial profit about 3 times, new technological process has prospects for commercial application.
Accompanying drawing explanation
What accompanying drawing 1 was the present invention is settled out crude product curpic carbonate process chart.
Accompanying drawing 2 is the wet product curpic carbonate washing flow figure of the present invention.
Accompanying drawing 3 is that the wet product curpic carbonate of the present invention adds hydrochloric acid and is converted into copper chloride process chart.
Accompanying drawing 4 is the copper chloride solution anhydrous cupric chloride flow chart of the present invention.
Accompanying drawing 5 is the copper chloride solution copper chloride dihydrate flow chart of the present invention.
Accompanying drawing 6 is the crude product curpic carbonate preparation facilities structural representation of the present invention.
Accompanying drawing 7 is the crude product curpic carbonate wash mill structural representation of the present invention.
Accompanying drawing 8 is the copper chloride solution anhydrous cupric chloride apparatus structure schematic diagram of the present invention.
Accompanying drawing 9 is the copper chloride solution copper chloride dihydrate apparatus structure schematic diagram of the present invention.
Detailed description of the invention
The present invention is further illustrated with embodiment below in conjunction with the accompanying drawings.
As shown in Fig. 1 ~ Fig. 5, a kind of method utilizing wiring board acidic etching waste liquid to reclaim copper resource, it contains with wiring board
Copper acidic etching waste liquid is raw material, joins sodium carbonate slip under room temperature and stirring condition, is settled out crude product curpic carbonate, filters
After separating crude product curpic carbonate, after water fully washs, add hydrochloric acid transfer copper chloride to, directly prepare anhydrous chlorination with spray drying method
Copper, or distillation and concentration, crystallize out copper chloride dihydrate product；Particularly as follows:
Step one, prepares sodium carbonate slip: under room temperature and stirring condition, in retort, adds required aqueous sodium carbonate
Later filtrate, makes sodium carbonate slip；
Step 2, is settled out crude product curpic carbonate: under agitation, at ambient temperature that the desired amount of wiring board cupric is acid
Etching waste liquor is slowly added to or in porous distributor pipe flows into sodium carbonate slip, forms crude product curpic carbonate precipitation, terminal point control
PH6-8, after adding, is stirred for；
Step 3, filters and separates crude product curpic carbonate: the crude product curpic carbonate that will make, and considers liquid with thick by filtration system isolated
Product curpic carbonate；
Step 4, wet product curpic carbonate washs: crude product curpic carbonate, after water wash system eluting, filtration and wash water, obtains wet product carbonic acid
Copper, in its wet product curpic carbonate, sodium content is less than 0.1%；
Step 5, wet product curpic carbonate adds hydrochloric acid and is converted into copper chloride: the wet product curpic carbonate after scrubbed adds concentrated hydrochloric acid, stirs molten
Copper chloride solution is obtained after solution, its acidity PH1-2, filters and separates a small amount of insoluble matter, keep a small amount of acidity, desirably prevent chlorination
The hydrolysis of copper；
Step 6, prepares copper chloride product: method one, prepares anhydrous chlorine containing refined copper chloride solution by spray drying device
Change copper；Method two, containing refined copper chloride solution by distillation and concentration, under 26-42 degree Celsius, crystallisation by cooling, then passed through
Filter system prepares copper chloride dihydrate product, and after filtration, remaining copper chloride solution returns and is again prepared two water by the method two
Copper chloride product.The sodium carbonate slip used is the one in sodium carbonate potassium carbonate sodium bicarbonate or its mixture.Crude product carbon
Acid copper is only stirred at room temperature washing with water, washes sodium in rear wet product curpic carbonate and can reach management and control requirement.Described crude product curpic carbonate washs
After add concentrated hydrochloric acid, change into fine copper chloride product, its purity reaches more than 98.0%.The worry liquid obtained in step 3, a part is made
It is back to crude product curpic carbonate processed by slurrying for later filtrate, a part of by preparation oxidant reuse circuit board etching line.
As shown in Fig. 6 ~ Fig. 9, wiring board acidic etching waste liquid is utilized to reclaim copper resource for implementing the one of above-mentioned technique
Equipment, it includes that the crude product curpic carbonate preparation facilities, crude product curpic carbonate wash mill and the copper chloride that set gradually by station produce
Product preparation facilities；Described crude product curpic carbonate preparation facilities includes reactor 10, slush pump A11, agitator tank A12, filtration system
A13, residue collection groove A14 and worry liquid collecting tank A15, described slush pump A11 are connected between reactor 10 and agitator tank A12,
Agitator tank A12 connects filter system A, and filter system A connects residue collection groove A14 and considers liquid collecting tank A15；Described reactor 10 is arranged
There is porous distributor pipe；Described crude product curpic carbonate wash mill includes agitator tank B120, slurry pump B 21, agitator tank B222, filters system
System B23, residue collection groove B24 and consider liquid collecting tank B25, described slurry pump B 21 connect agitator tank B120 and agitator tank B222 it
Between, agitator tank B222 connects filter system B, and filter system B connects residue collection groove B24 and considers liquid collecting tank B25；Described copper chloride produces
Product preparation facilities is copper chloride solution anhydrous cupric chloride device or copper chloride solution copper chloride dihydrate device；Described copper chloride
Solution anhydrous cupric chloride device includes reactor C30, kinetic pump C131, fine filtering apparatus C32, copper chloride liquid storage tank C33, moves
Power pump C234, heat blower 34, spray dryer 35, anhydrous cupric chloride packing device 36, described kinetic pump C131 is connected to
Between reactor C30 and fine filtering apparatus C32, fine filtering apparatus C32 connects copper chloride liquid storage tank C33, kinetic pump C234 and connects
Between copper chloride liquid storage tank C33 and spray dryer 35, heat blower 34 connects spray dryer 35, spray dryer 35
Connect anhydrous cupric chloride packing device 36；Described copper chloride solution copper chloride dihydrate device includes reactor D40, kinetic pump
D41, fine filtering apparatus D42, distillation and concentration device 43, filtration system D44, copper chloride dihydrate packing device 45, described kinetic pump D41
Being connected between reactor D40 and fine filtering apparatus D42, defecator D connects distillation and concentration device 43, and distillation and concentration device 43 connects
Filtration system D44, filtration system D44 connects copper chloride dihydrate packing device 45.Preferably, described agitator tank A12, agitator tank
B120, the mixing apparatus of slurry pump B 21 can be the one in mechanical agitation, bubbling stirring or vibrations mixing apparatus.Preferably,
Institute's filtration system B23 can be vacuum filter, pressure filter, centrifuge, filter medium can be sand core filter plate, ceramic filtering plate,
Filter cloth or Organic substance height filter press plate, centrifuge can be Horizontal helical type centrifuge, flat or 3-foot automatic discharge centrifuge.
Example one,
As a example by acid etching, its acidic etching liquid copper concentration 130g/L, acidity 2.0N.1 side's acidic etching liquid is sunk by slurrying
After copper separates, consuming 0.286 ton of sodium carbonate, obtain 0.428 ton of crude product carbonic acid, its heavy copper rate reaches 99.9%.
Example two,
Acidic etching liquid by acidic etching liquid by heavy copper after, obtain crude product curpic carbonate, through water elution, sodium in its wet product curpic carbonate
Containing 0.1%.Molten wet product curpic carbonate is returned with concentrated hydrochloric acid, its PH 2.0, filters and removes a small amount of insoluble matter, prepare copper chloride solution.Take chlorine
Changing copper solution, dry prepared anhydrous cupric chloride, its product quality is: anhydrous cupric chloride purity 98%, sodium 0.2%, ferrum 14ppm, lead
8.2 ppm, chromium 7.8 ppm, cadmium 4.7 ppm, arsenic 4.6 ppm, nickel 4.2 ppm.
Example three,
Acidic etching liquid by acidic etching liquid by heavy copper after, obtain crude product curpic carbonate, through water elution, sodium in its wet product curpic carbonate
Containing 0.1%.Molten wet product curpic carbonate is returned with concentrated hydrochloric acid, its PH 2.0, filters and removes a small amount of insoluble matter, prepare copper chloride solution.Take chlorine
Change copper solution, distillation and concentration to supersaturation, under 30 degree, stir crystallisation by cooling, filter to obtain copper chloride dihydrate.Its product quality
For: copper chloride dihydrate 98.40%, sodium 632ppm.
1, in heavy copper part, equipment to install narrow meshed coil pipe distributor, makes the addition of acidic etching liquid uniformly to subtract
Form peritectoid phenomenon less.
2, with spray drying method, when copper chloride mother solution uses spray drying technology can produce granule copper chloride. make speed of production fast,
And be carried out continuously, the hydrolysis preventing copper chloride or the decomposition caused because of hot-spot, thus ensure product quality. also improve behaviour
Make environment.
To control well when 3, crystallizing copper chloride dihydrate and crystallize and air-dried temperature, because these product form different water in different temperature
Compound.
In sum, the present invention provides one from the easy method all reclaiming copper resource of acidic etching waste liquid, its feature
Be by heavy copper sink copper equipment add carbonic acid alkali precipitation go out crude product curpic carbonate, copper rate of deposition reaches 99.9%, easily filters, filter
Liquid part turns one's head dosing, and remaining reuse reaches zero-emission.Various fine copper product can be processed into after crude product curpic carbonate is scrubbed, as
Copper chloride, copper oxide, copper sulfate, basic copper carbonate, copper nitrate copper bromide cupric oxalate etc..Present invention process is simple, green ring
Protecting, low cost, reduced investment, equipment is domestic to be available for, and can increase profit 2.4 ten thousand yuan at wiring board Endogenous copper.
The above is only the better embodiment of the present invention, thus all according to the structure described in present patent application scope,
The equivalence that feature and principle are done changes or modifies, in the range of being all included in present patent application.
Claims (8)
1. one kind utilizes the method that wiring board acidic etching waste liquid reclaims copper resource, it is characterised in that: it is with wiring board keto-acid containing
Property etching waste liquor be raw material, under room temperature and stirring condition, join sodium carbonate slip, be settled out crude product curpic carbonate, filter and separate
After crude product curpic carbonate, after water fully washs, add hydrochloric acid transfer copper chloride to, directly prepare anhydrous cupric chloride with spray drying method, or
Distillation and concentration, crystallizes out copper chloride dihydrate product；Particularly as follows:
Step one, prepares sodium carbonate slip: under room temperature and stirring condition, in retort, adds required aqueous sodium carbonate
Later filtrate, makes sodium carbonate slip；
Step 2, is settled out crude product curpic carbonate: under agitation, at ambient temperature that the desired amount of wiring board cupric is acid
Etching waste liquor is slowly added to or in porous distributor pipe flows into sodium carbonate slip, forms crude product curpic carbonate precipitation, terminal point control
PH6-8, after adding, is stirred for；
Step 3, filters and separates crude product curpic carbonate: the crude product curpic carbonate that will make, and considers liquid with thick by filtration system isolated
Product curpic carbonate；
Step 4, wet product curpic carbonate washs: crude product curpic carbonate, through water wash system, obtains wet product curpic carbonate, in its wet product curpic carbonate
Sodium content is less than 0.1%；
Step 5, wet product curpic carbonate adds hydrochloric acid and is converted into copper chloride: the wet product curpic carbonate after scrubbed adds concentrated hydrochloric acid, stirs molten
Copper chloride solution is obtained after solution, its acidity PH1-2, filters and separates a small amount of insoluble matter, keep a small amount of acidity, desirably prevent chlorination
The hydrolysis of copper；
Step 6, prepares copper chloride product: method one, prepares anhydrous chlorine containing refined copper chloride solution by spray drying device
Change copper；Method two, containing refined copper chloride solution by distillation and concentration, under 26-42 degree Celsius, crystallisation by cooling, then passed through
Filter system prepares copper chloride dihydrate product.
A kind of method utilizing wiring board acidic etching waste liquid to reclaim copper resource the most according to claim 1, its feature exists
In: the sodium carbonate slip used is the one in sodium carbonate potassium carbonate sodium bicarbonate or its mixture.
A kind of method utilizing wiring board acidic etching waste liquid to reclaim copper resource the most according to claim 1, its feature exists
In: crude product curpic carbonate is only stirred at room temperature washing with water, washes sodium in rear wet product curpic carbonate and can reach management and control requirement.
A kind of method utilizing wiring board acidic etching waste liquid to reclaim copper resource the most according to claim 1, its feature exists
In: adding concentrated hydrochloric acid after the washing of described crude product curpic carbonate, change into fine copper chloride product, its purity reaches more than 98.0%.
A kind of method utilizing wiring board acidic etching waste liquid to reclaim copper resource the most according to claim 3, its feature exists
In: the worry liquid obtained in step 3, a part is back to crude product curpic carbonate processed as later filtrate by slurrying, and some is passed through
Preparation oxidant reuse circuit board etching line.
6. one kind utilizes the equipment that wiring board acidic etching waste liquid reclaims copper resource, it is characterised in that: it includes by station successively
Crude product curpic carbonate preparation facilities, crude product curpic carbonate wash mill and the copper chloride product preparation facilities arranged；
Described crude product curpic carbonate preparation facilities includes reactor (10), slush pump A(11), agitator tank A(12), filtration system A
(13), residue collection groove A(14) and consider liquid collecting tank A(15), described slush pump A(11) be connected to reactor (10) and agitator tank
A(12) between, agitator tank A(12) connect filter system A, filter system A connects residue collection groove A(14) and consider liquid collecting tank A(15)；
Described reactor (10) is provided with porous distributor pipe；
Described crude product curpic carbonate wash mill includes agitator tank B1(20), slurry pump B (21), agitator tank B2(22), filtration system B
(23), residue collection groove B(24) and consider liquid collecting tank B(25), described slurry pump B (21) connects agitator tank B1(20) and agitator tank
B2(22) between, agitator tank B2(22) connect filter system B, filter system B connects residue collection groove B(24) and consider liquid collecting tank B
(25)；
Described copper chloride product preparation facilities is copper chloride solution anhydrous cupric chloride device or copper chloride solution system two water chlorination
Copper device；
Described copper chloride solution anhydrous cupric chloride device includes reactor C(30), kinetic pump C1(31), fine filtering apparatus C
(32), copper chloride liquid storage tank C(33), kinetic pump C2(34), heat blower (34), spray dryer (35), anhydrous cupric chloride
Packing device (36), described kinetic pump C1(31) it is connected to reactor C(30) and fine filtering apparatus C(32) between, essence filters dress
Put C(32) connect copper chloride liquid storage tank C(33), kinetic pump C2(34) it is connected to copper chloride liquid storage tank C(33) and spray dryer
(35) between, heat blower (34) connects spray dryer (35), and spray dryer (35) connects anhydrous cupric chloride packaging dress
Put (36)；
Described copper chloride solution copper chloride dihydrate device includes reactor D(40), kinetic pump D(41), fine filtering apparatus D
(42), distillation and concentration device (43), filtration system D(44), copper chloride dihydrate packing device (45), described kinetic pump D(41) connect
In reactor D(40) and fine filtering apparatus D(42) between, defecator D connects distillation and concentration device (43), distillation and concentration device (43)
Connect filtration system D(44), filtration system D(44) connect copper chloride dihydrate packing device (45).
A kind of equipment utilizing wiring board acidic etching waste liquid to reclaim copper resource the most according to claim 6, its feature exists
In: described agitator tank A(12), agitator tank B1(20), the mixing apparatus of slurry pump B (21) can be mechanical agitation, bubbling stirring
Or the one in vibrations mixing apparatus.
A kind of equipment utilizing wiring board acidic etching waste liquid to reclaim copper resource the most according to claim 7, its feature exists
In: institute's filtration system B(23) can be vacuum filter, pressure filter, centrifuge, filter medium can be sand core filter plate, pottery
Filter plate, filter cloth or Organic substance height filter press plate, centrifuge can be Horizontal helical type centrifuge, flat or 3-foot automatic discharging centrifugal
Machine.
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| CN112143265A (en) * | 2019-06-28 | 2020-12-29 | 铜陵富翔铜再生循环利用有限公司 | Method for preparing carbon black and co-producing copper chloride by using waste enameled wire |
| CN112143265B (en) * | 2019-06-28 | 2022-03-22 | 铜陵富翔铜再生循环利用有限公司 | Method for preparing carbon black and co-producing copper chloride by using waste enameled wire |
| CN110921695A (en) * | 2019-12-20 | 2020-03-27 | 广东臻鼎环境科技有限公司 | Method for recycling alkaline etching waste liquid |
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