CN107761140A - Tin plating solution purification equipment and its purification method - Google Patents
Tin plating solution purification equipment and its purification method Download PDFInfo
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- CN107761140A CN107761140A CN201610686978.7A CN201610686978A CN107761140A CN 107761140 A CN107761140 A CN 107761140A CN 201610686978 A CN201610686978 A CN 201610686978A CN 107761140 A CN107761140 A CN 107761140A
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- Prior art keywords
- plating solution
- tin
- tin plating
- settling tank
- cleaner
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/30—Electroplating: Baths therefor from solutions of tin
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention discloses a kind of technology of tin plating solution purification and equipment, its method to be:Tin plating solution containing solid and ionic impurity and cleaner are placed in retort after reacting certain time, reaction solution carries out separation of solid and liquid by settling tank, tin plating solution is after settling tank settles, plating solution after purification is back to tin plating solution storage tank, and sediment is used as solid waste discharge after filter press press filtration.The purifier system has stronger purification capacity, can effectively remove tin mud and ionic impurity (particularly Pb ions) in plating solution, meets the production requirement of high-quality K plates.Requirement of the tin plating unit to tin raw material can be reduced using the device simultaneously, the tin plate of high-quality can be produced using the tin raw material of conventional 99.9% purity, there is notable cost efficiency.
Description
Technical field
The present invention relates to the production of metallurgy industry tin plate, particularly suitable in insoluble anode technique tin plating solution it is net
Change, solid and ionic species impurity in plating solution can effectively be reduced by inventing involved technique and equipment, so as to ensure that high-quality is tin plating
The production of plate.
Background technology
Tin plate is the main packaging material of food packaging industry, and the quality of tin plate depends mainly on the tin plating of plate surface
Layer.Tin plating process is an electrochemical reaction process, in this electrochemical process, the Sn in plating solution2+It is reduced into negative electrode
Sn atomic depositions are on the surface of strip, so as to obtain tin plate.Therefore during electrotinning, the performance of tin plate and plating solution
Count for much, and the clean-up performance of tin plating electrolyte is an important performance indexes of tin plating electrolyte, wherein the content of tin mud is to plating fluidity
It can influence great.
Anode during tin plating then can be divided into soluble anode and insoluble anode according to the difference of tin plating technique, solvable
Property anode use tin slab, Sn atoms are oxidized in electroplating process, form Sn2+Ion enters plating solution, the Sn in plating solution2+In the moon
Pole is reduced the surface for being deposited on strip, forms tin plate;In insoluble anode technique, the electrochemical reaction that anode occurs is
OH in plating solution-Ion is oxidized, generation oxygen, and the Sn in plating solution2+Then come from the molten tin system outside tin plating unit,
In molten tin system, the dissolving of tin occurs in the case of logical oxygen for plating solution, forms Sn2+。
For insoluble anode, the oxygen being added in electroplating process during caused oxygen and molten tin in system can add
The Sn of acute plating solution2+Oxidation forms Sn4+, tin mud is a kind of SnO2Hydrate, it is by the Sn in plating solution2+By further rear oxygen
Metaplasia into, it is characterized in that fine size, there is certain viscosity.The generation of tin mud is mainly the Sn in plating solution2+With oxidant (oxygen and
Fe3+) contact generation, the tin mud in plating solution is in Sn2+The surface of strip will be co-deposited in Ion deposition processes, its consequence one
Aspect influences the compactness of coating in itself, on the other hand easily causes tin plating layer surface to form grey black, has influence on tin-plated board corrosion-resistance
With covering with paint property.For the tin mud in plating solution, current minimizing technology is filtered using filter, but due to the granularity of tin mud
Carefully, while viscosity is larger, is easy to using the method for filtering so that filter cloth blocks, filtering is difficult to obtain good effect.
The impurity element (such as Pb, Cd, As, Fe) in tin raw material will be also entered in plating solution with the dissolving of tin simultaneously, this
A little impurity elements enter will cause important influence to the performance of coating in coating so that tin plate can not meet high-quality
The requirement of tin plate.Such as EU criteria, " EN10333-2005 is packed for the food that steel-be intended for contacts human and animal's diet
Or flat steel product-tin plate of beverage " in provide in the tin slab for tin-plated product that total tin is more than 99.85%, lead content is less than
0.01%, it is less than 0.01% every content, arsenic content is less than 0.03%.It is raw at present to produce the tin plate of low impurity content
The tin raw material that factory uses low impurity content is produced, this will greatly increase tin plating cost, reduces the competitiveness of product in market.
For the minimizing technology of impurity in plating solution, CN200710068328.7 discloses one kind and staticized for nickelous sulfate plating liquid
Technology and equipment, it is made up of pre-reaction zone, high-order water distributing area, static water conservancy diversion settling zone, buffering area, microstrainer etc.,
Impurity and the aging micelles such as copper in plating solution, iron, zinc can effectively be removed.The mode of this purification plating solution is not suitable for removing plating
Tin mud and lead impurity in solution of tin.CN201310142493.8 and CN201020255883.8 proposes the method using filtering
To purify plating solution, but because the tin mud pellet degree of tin plating solution is small, sticky big, it is easy to block screen pack, therefore filter efficiency is low, more
The foreign ion in plating solution, such as lead ion can not be removed.CN201420365262.3 and CN201220361976.8 are then proposed
The device of lead impurity in plating solution is removed using the method for electrolysis, because the internal circulating load of continuous electroplating tin unit plating solution is big, use is low
Current density electrolysis efficiency is low, can not meet production requirement.
Clean plating solution is the premise for producing high-quality tin plate, for continuous electroplating tin unit, due to currently used for net
The technique and method of change plating solution are also immature, and the technique for being suitable for tin plating solution purification and equipment are developed for this to improving tin plate
Quality it is significant and effect.
The content of the invention
The purpose of this patent, which is that invention is a kind of, while can effectively remove the apparatus and method of impurity solid and ion in plating solution,
Involved equipment includes retort, settling tank and separation equipment, and involved method includes the configuration of cleaner, removal of impurities instead
It, should settle and separation, the present invention can realize the steady production of high-quality tin plate, particularly effectively reduce tin plating layer surface
Lead content in grey black and coating.
The present invention is achieved by the following technical solutions:
A kind of tin plating solution purification equipment, it includes:Bath trough, bath filter device, settling tank, filter press and retort,
The bath trough, bath filter device, retort, settling tank are sequentially communicated the water flow circuits to form a closure, the filter press
It is connected with settling tank, and the water flow circuits of another closure is formed with bath trough, bath filter device, retort.
Preferably, the retort is also connected with a cleaner preparation tank.
Preferably, the retort includes reacting tank body, cleaner distributor, agitating paddle, plating solution entrance and plating
Liquid is exported, and the cleaner distributor is arranged inside reacting tank body, and the agitating paddle is arranged at the lower section of cleaner distributor,
Plating solution entrance and the plating solution outlet is respectively arranged at the bottom and top of reacting tank body.
Preferably, the agitating paddle is flat paddle structure, and the width W of agitating paddle is (the 1/3~1/ of tank diameter D1
2)。
Preferably, the settling tank includes settling tank, center down-comer, purified liquor outlet and sludge outlet, institute
Stating settling tank includes direct tube section and is integrally connected to the conical section of the direct tube section, and the center down-comer is arranged at settling tank
The direct tube section oral area of body, the purified liquor outlet are arranged at direct tube section side wall upper part, and the sludge outlet is arranged at the end of conical section
End, and the diameter D2 of the direct tube section is numerically equal to tin plating solution flow F1 (1/3~1/2), direct tube section H height is
1.2~2.0 times of D2.
Preferably, the center down-comer includes the body of cylinder and the taper of integrally connected and bottom of the pipe
The mouth of pipe, the diameter d of body are numerically equal to tin plating solution flow F1 (1/50~1/100), and nozzle diameter B is (the 3 of d
~5) again.
Preferably, there is nylon filter cloth, the mesh number of the nylon filter cloth is 200 mesh in the filter press.
A kind of purification method based on foregoing tin plating solution purification equipment, it comprises the following steps:
Cleaner at tin plating solution and 70~80 DEG C is passed through after being reacted in retort, reaction solution is passed through precipitation
Settled in tank;
The supernatant liquor isolated after sedimentation is transferred back in bath trough by way of overflow, precipitation is squeezed into filter press
Middle carry out press filtration, isolates clear liquid and mud cake, the clear liquid is transferred back in bath trough, using the mud cake as solid waste
Discharge;
Wherein, there is preferably removal of impurities performance to react the barium sulfate generated, the cleaner is to contain ethanol
Baryta water.The volume content 1~5% of ethanol, meanwhile, the mass fraction of baryta water is 2.5%.
In general, the treating capacity of the cleaning equipment determines according to the total amount of plating solution in tin plating unit, unit hour
Treating capacity is (1/15~1/10) of plating solution total amount.
The addition of cleaner is 0~100L/h, and cleaner conveyance conduit needs to set heat-insulation layer, and cleaner passes through nozzle
It is added in plating solution, the reaction time of cleaner and plating solution in retort was at 0.5~1.0 hour.
Preferably, the depth h of the center down-comer intercalation reaction liquid liquid level is (1/3~3/5) H.
The beneficial effects of the present invention are:
1st, for continuous electroplating tin unit, the tin mud and foreign ion (such as Pb, As, Cd) in plating solution can be effectively reduced, is filled
To put after continuously running 12 hours, the tin mud in plating solution removable 70%, the Pb foreign ions in plating solution can be reduced to below 5ppm,
So as to meet the production requirement of high-quality tin plate;
2nd, the solid and type impurity ion in tin plating solution can be effectively removed, requirement of the unit to tin raw material is greatly reduced,
The steady production of high-quality tin plate can be met using the tin raw material of 99.9 qualities;
3rd, the lead ion content in plating solution can be effectively reduced, for can be effective in the K plate continuous flow procedures of high tin coating weight
The lead content in coating is reduced, can reach the control lead requirement in international advanced standard.Simultaneously because plating solution has obtained effectively only
Change, the tin cement content in plating solution is greatly reduced, and advantageously ensures that the compactness of thickness coating, reduces the iron solution value and ATC of K plates
Value, the corrosion resistance of K plates is improved, realize the steady production of K plates.
Brief description of the drawings
The detailed description made by reading with reference to the following drawings to non-limiting example, further feature of the invention,
Objects and advantages will become more apparent upon:
Fig. 1 is the structural representation of the tin plating solution purification equipment of the present invention;
Fig. 2 is the structural representation of retort in the present invention;
Fig. 3 is the structural representation of settling tank in the present invention;
In figure:1st, bath trough;2nd, bath filter device;3rd, retort;4th, settling tank;5th, filter press;6th, cleaner preparation tank;
7th, filtrate cycle pump;8th, slush pump;9th, measuring pump;31st, agitating paddle;32nd, cleaner distributor;33rd, plating solution entrance;34th, plating solution
Outlet;35th, reacting tank body;41st, settling tank;42nd, center down-comer;43rd, purified liquor outlet;44th, sludge outlet.
Embodiment
With reference to specific embodiment, the present invention is described in detail.Following examples will be helpful to the technology of this area
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill to this area
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection domain.
As shown in Figures 1 to 3, a kind of tin plating solution purification equipment provided by the invention includes:Bath trough 1, bath filter device
2nd, retort 3, settling tank 4 and filter press 5, bath trough 1, bath filter device 2, retort 3, settling tank 4 are sequentially communicated to form one
The water flow circuits of bar closure, filter press 5 is connected with settling tank 4, and is formed separately with bath trough 1, bath filter device 2, retort 3
The water flow circuits of one closure.
Because cleaner typically selects baryta water, in order to prevent cleaner from precipitating, retort 3 is also with one
Cleaner preparation tank 6 is connected.
Retort 3 includes reacting tank body 35, cleaner distributor 32, agitating paddle 31, plating solution entrance 33 and plating solution outlet 34,
Cleaner distributor 32 is arranged inside reacting tank body 35, and agitating paddle 31 is arranged at the lower section of cleaner distributor 32, and plating solution enters
Mouth 33 and plating solution outlet 34 are respectively arranged at the bottoms and top of reacting tank body.Cleaner can be entered anti-by cleaner distributor
Answer in tank, to ensure that cleaner is dispersed in retort.
Agitating paddle 31 is flat paddle structure, and the width W of agitating paddle is tank diameter D1 (1/3~1/2).
Settling tank 4 includes settling tank 41, center down-comer 42, purified liquor outlet 43 and sludge outlet 44, settling tank 41
Including direct tube section and the conical section for being integrally connected to the direct tube section, center down-comer 42 is arranged at the direct tube section mouth of settling tank
Portion, the purified liquor outlet are arranged at direct tube section side wall upper part, and the sludge outlet is arranged at the end of conical section, and the straight tube
The diameter D2 of section is numerically equal to tin plating solution flow F1 (1/3~1/2), and the height for leading directly to section H is the 1.2~2.0 of D2
Times.
The diameter d of center down-comer is numerically equal to tin plating solution flow F1 (1/50~1/100), center down-comer
Lower end it is tapered, and the lower port diameter B of down-comer is d (3~5) times.
There is nylon filter cloth, the mesh number of the nylon filter cloth is 200 mesh in filter press.
Embodiment
Certain tin plating unit production line for producing 200000 tons per year uses PSA insoluble anode techniques, due to insoluble anode technique
Sn in plating solution2+Tin ion comes from molten tin system, and oxygen blast is needed during molten tin, Sn in oxygen blown process aggravation plating solution2+
It is oxidized to Sn4+So that tin mud amount is exceeded for a long time in plating solution.Simultaneously because plating solution is recycled for a long time, the lead ion in tin raw material
Constantly accumulation in the plating solution, the production requirement of high-quality K plates can not be met, tin plating electrolyte is carried out only using the art of this patent for this
Change is handled, and the scheme of specific implementation is:
1st, tin plating solution cleaner is the barium hydroxide solution of the concentration ethanol containing 2v/v%, and the temperature of barium hydroxide solution is
75 DEG C, cleaner is prepared with analysis pure cerium hydroxide barium.
2nd, for plating solution purifier using the technological process shown in Fig. 1, internal circulating load of the plating solution in purifier is 5m3/h。
3rd, the preparation of cleaner is carried out in preparing tank, and the volume of preparing tank is 2m3, carrying vapour heating jacket, material is
316L stainless steels, the material of cleaner pipeline use PPH.
3rd, cleaner is added in retort by measuring pump with 50L/h flow, is calculated by the reaction time of 1 hour,
The volume of retort is 5m3, the agitating paddle in retort uses flat paddle, and the width d of agitating paddle is 600mm, the rotating speed of agitating paddle
For 60rpm.
4th, the plating solution after reacted enters the center down-comer of settling tank by way of overflow, and plating solution is in settling tank
After stopping about 4 hours, clear liquid is back to by way of overflow in plating solution circulating slot, and the precipitum at settling tank bottom uses slush pump
Take away.
5th, slush pump start and stop are controlled by settling the differential manometer of pot bottom, when differential manometer detects that pressure exceedes initial value
After 10%, the sediment of bottom is extracted into filter press by mud pump startup, and filter press uses nylon filter cloth, and the mesh number of filter cloth is
200 mesh.
The tin plating unit is using the technology described in this patent, 85m in unit3Plating solution is through 12 hours continuous cycle down lead, plating
Tin cement content drops to below 1.5g/L from 2.5g/L in liquid, and the lead content in plating solution drops to 3ppm from 20ppm.Using this
The tin plate of plating solution production, the content of lead is less than 100ppm in its tin coating, meets the production requirement of high-quality K plates.
The unit is former to produce tin plate, after the technology and equipment of the patent, unit using 99.99% high purity tin
Tin raw material requirement is reduced to 99.9%, and the reduction of raw material requirement make it that the production cost of tin-plated product is greatly reduced, and takes
Obtain significant economic benefit.
In summary, only presently preferred embodiments of the present invention, is not used for limiting the scope that the present invention is implemented, it is all according to
The equivalent changes and modifications carried out by shape, construction, feature and spirit described in scope of the invention as claimed, this all should be included in
In the right of invention.
Claims (9)
- A kind of 1. tin plating solution purification equipment, it is characterised in that including:Bath trough, bath filter device, settling tank, filter press and Retort, the bath trough, bath filter device, retort, settling tank are sequentially communicated the water flow circuits to form a closure, described Filter press is connected with settling tank, and the water flow circuits of another closure are formed with bath trough, bath filter device, retort.
- 2. tin plating solution purification equipment as claimed in claim 1, it is characterised in that the retort is also prepared with a cleaner Tank is connected.
- 3. tin plating solution as claimed in claim 1 or 2 purification equipment, it is characterised in that the retort include reacting tank body, Cleaner distributor, agitating paddle, plating solution entrance and plating solution outlet, the cleaner distributor are arranged inside reacting tank body, institute The lower section that agitating paddle is arranged at cleaner distributor is stated, plating solution entrance and the plating solution outlet is respectively arranged under reacting tank body Portion and top.
- 4. tin plating solution purification equipment as claimed in claim 3, it is characterised in that the agitating paddle agitating paddle is flat paddle knot Structure, the width W of agitating paddle are tank diameter D1 (1/3~1/2).
- 5. tin plating solution as claimed in claim 1 purification equipment, it is characterised in that the settling tank include settling tank, in Heart down-comer, purified liquor outlet and sludge outlet, the settling tank include direct tube section and are integrally connected to the cone of the direct tube section Shape section, the center down-comer are arranged at the direct tube section oral area of settling tank, and the purified liquor outlet is arranged in direct tube section side wall Portion, the sludge outlet is arranged at the end of conical section, and the diameter D2 of the direct tube section is numerically equal to tin plating solution stream F1 (1/3~1/2) is measured, the height for leading directly to section H is 1.2~2.0 times of D2.
- 6. tin plating solution purification equipment as claimed in claim 5, it is characterised in that the diameter d of the center down-comer is in number It is equal to tin plating solution flow F1 (1/50~1/100) in value, the lower end of center down-comer is tapered, and the pipe of center down-comer (3~5) times that mouth diameter B is d.
- 7. tin plating solution purification equipment as claimed in claim 1, it is characterised in that there is nylon filter in the filter press Cloth, the mesh number of the nylon filter cloth is 200 mesh.
- 8. a kind of purification method of the tin plating solution purification equipment based on described in any one in claim 1~7, its feature exist In comprising the following steps:Cleaner at tin plating solution and 70~80 DEG C is passed through after being reacted in retort, reaction solution is passed through in settling tank Settled;The supernatant liquor isolated after sedimentation is transferred back in bath trough by way of overflow, precipitation is squeezed into filter press Row press filtration, isolates clear liquid and mud cake, and the clear liquid is transferred back in bath trough, is arranged the mud cake as solid waste Put;Wherein, the cleaner is the baryta water containing ethanol.
- 9. purification method as claimed in claim 8, it is characterised in that the depth of the center down-comer intercalation reaction liquid liquid level H is (1/3~3/5) H.
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CN201610686978.7A CN107761140A (en) | 2016-08-18 | 2016-08-18 | Tin plating solution purification equipment and its purification method |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114277416A (en) * | 2020-09-28 | 2022-04-05 | 上海梅山钢铁股份有限公司 | Production method and equipment of low-lead-content tin plate with methanesulfonic acid coating of insoluble anode |
CN117210925A (en) * | 2023-11-07 | 2023-12-12 | 无锡釜川科技股份有限公司 | Electrotinning electrolyte circulating system and control method thereof |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101838073A (en) * | 2009-03-20 | 2010-09-22 | 宝山钢铁股份有限公司 | Silicon steel alkali purification method and device |
CN104213183A (en) * | 2013-05-30 | 2014-12-17 | 宝钢工程技术集团有限公司 | Acidic electrotinning liquid lead ion processing method |
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2016
- 2016-08-18 CN CN201610686978.7A patent/CN107761140A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101838073A (en) * | 2009-03-20 | 2010-09-22 | 宝山钢铁股份有限公司 | Silicon steel alkali purification method and device |
CN104213183A (en) * | 2013-05-30 | 2014-12-17 | 宝钢工程技术集团有限公司 | Acidic electrotinning liquid lead ion processing method |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114277416A (en) * | 2020-09-28 | 2022-04-05 | 上海梅山钢铁股份有限公司 | Production method and equipment of low-lead-content tin plate with methanesulfonic acid coating of insoluble anode |
CN117210925A (en) * | 2023-11-07 | 2023-12-12 | 无锡釜川科技股份有限公司 | Electrotinning electrolyte circulating system and control method thereof |
CN117210925B (en) * | 2023-11-07 | 2024-03-08 | 无锡釜川科技股份有限公司 | Electrotinning electrolyte circulating system and control method thereof |
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