CN109534575A - A kind of lossless regeneration and treatment technique of PCB tin-stripping wastewater - Google Patents
A kind of lossless regeneration and treatment technique of PCB tin-stripping wastewater Download PDFInfo
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- CN109534575A CN109534575A CN201811590568.8A CN201811590568A CN109534575A CN 109534575 A CN109534575 A CN 109534575A CN 201811590568 A CN201811590568 A CN 201811590568A CN 109534575 A CN109534575 A CN 109534575A
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- 238000000034 method Methods 0.000 title claims abstract description 55
- 230000008929 regeneration Effects 0.000 title claims abstract description 25
- 238000011069 regeneration method Methods 0.000 title claims abstract description 25
- 239000002351 wastewater Substances 0.000 title claims abstract description 22
- 238000011282 treatment Methods 0.000 title claims abstract description 15
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 79
- 239000007788 liquid Substances 0.000 claims abstract description 62
- 239000002699 waste material Substances 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- 230000000694 effects Effects 0.000 claims abstract description 18
- 230000008901 benefit Effects 0.000 claims abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052802 copper Inorganic materials 0.000 claims abstract description 14
- 239000010949 copper Substances 0.000 claims abstract description 14
- 229910000679 solder Inorganic materials 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 10
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 27
- 238000000926 separation method Methods 0.000 claims description 20
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 18
- 229910017604 nitric acid Inorganic materials 0.000 claims description 18
- 238000004821 distillation Methods 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 239000012530 fluid Substances 0.000 claims description 10
- 239000004615 ingredient Substances 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 8
- 238000005292 vacuum distillation Methods 0.000 claims description 8
- 239000012141 concentrate Substances 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- 230000007613 environmental effect Effects 0.000 claims description 5
- 238000005259 measurement Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000011161 development Methods 0.000 claims description 3
- 230000018109 developmental process Effects 0.000 claims description 3
- 239000011814 protection agent Substances 0.000 claims description 3
- 239000013049 sediment Substances 0.000 claims description 3
- 230000003068 static effect Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 19
- 238000004064 recycling Methods 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 5
- 239000005749 Copper compound Substances 0.000 abstract description 2
- -1 metallic tin copper compound Chemical class 0.000 abstract description 2
- 229910001432 tin ion Inorganic materials 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 description 10
- 230000001376 precipitating effect Effects 0.000 description 9
- 239000003814 drug Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 238000012545 processing Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000011133 lead Substances 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 229910003654 H2SnO3 Inorganic materials 0.000 description 1
- 241000500881 Lepisma Species 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 230000004630 mental health Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000275 quality assurance Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
Abstract
The invention discloses a kind of lossless regeneration and treatment techniques of PCB tin-stripping wastewater, this technique is the lossless regeneration and treatment technique for being directed to PCB circuit board industry and move back tin-stripping wastewater caused by tin process, the metallic tin copper compound purity is high that technical process is extract from waste tin stripper, it makes a silk purse out of a sow's ear, and ensures to move back tin effect after tin stripper regeneration.Its technical process is suitable to efficiently separate agent by being added in the spent solder stripper to failure and make copper in spent solder stripper, tin ion after filtering with tin stripping liquid by being separated, keep the original useful chemical component of tin stripping liquid, again by being concentrated after a series of process flows such as adjustment parameter, enable the tin stripper of failure to recirculate utilization, and does not influence it and move back tin effect.The advantages that this technique does not contain singly simply, at low cost, easy to operate, and there are also zero-emission, the economic benefits of 100% recycling.
Description
Technical field
The present invention relates to technical field of waste water processing more particularly to a kind of lossless regeneration and treatment techniques of PCB tin-stripping wastewater.
Background technique
Because the needs of production technology can generate useless move back in the industries such as electronics and information industry (especially PCB industry) and plating
Tin liquor, harm is quite big, it has the characteristics that following:
Stanniferous, nitric acid amount height, harm are greatly, quantity is more and system is complicated: generation waste liquid amount is maximum in Tui Xishi PCB enterprise
One of process, every 1000 square metres of wiring boards of production generate 0.75 cubic metre of spent solder stripper, and China hardboard PCB in 2007 reaches
1.5 hundred million square metres, generate about 10 ten thousand stere of spent solder stripper.And the speed increase thrown away with 5%~8%.Heavy metal in waste liquid contains
Amount is more and high: tin up to 80-100g/L, copper 10-20g/L, there is also lead, nickel, silver etc. by iron 30-50g/L；Pollution index is high；Trip
It is big (acid equivalent of nitric acid is 5 or more) from acidacidity；Other organic compound species more (heterocyclic compounds, multiple ring fragrance
Compound, polymer etc.).
It is big to handle complicated and pollution solution difficulty: tenor is more in tin removal waste liquor and the high system of height, acidity is complicated, causes
It handles extremely difficult and complicated.The research except lead only only also is carried out to waste tin stripper in the world, but does not mention and how to remove
Tin and copper, the circular regeneration that less someone studies waste tin stripper use.So far still come without a feasible industrialization technology thorough
Bottom solves the problems, such as spent solder stripper environmental pollution.Although taking multistage transfer processing at present, not only energy consumption, at high cost and still have
Serious secondary pollution.There is very big harm to the mankind, biology and environment.
Distribution is wide: more than 2000 of China PCB scope of the enterprise is different, with middle-size and small-size on the high side, is distributed in 20 Lai Ge provinces and cities,
Middle south China accounts for 52%, and East China 35%, other areas account for about 13%.And south China accounts for the maximum Guangdong Province of share and is also quite dispersed in entirely
It saves domestic.
Due to above, the spent solder stripper generated in domestic PC B enterprise at present is directly or indirectly enterprise
In the water source and soil of industry location, great destruction is produced to local resources, people's physical and mental health is constituted seriously
Threat.
Tin stripping liquid technical principle: tin and its alloy have a metal bondings such as tin and copper, but can in strong acid rapidly-soluble spy
Property.Tin stripping liquid be exactly be formulated according to this characteristic, PCB enterprise technique require selectively dissolve copper electroplating layer on slicker solder and
Do not corrode copper-based bottom again, this with regard to danger spot must tin stripping liquid include and biggish move back tin capacity；Tin speed is moved back faster；Preferable copper
The characteristics such as protective value and preferable bright and clean performance.
Tin stripping liquid is divided into three types: i.e. fluoride type, nitric acid type, nitric acid-alkyl sulfonic acid type.Fluoride type is because of hydrogeneous fluorine
It is poor to environmental index and technical-economic index for acid, not salt (not change hydrogen ammonium), peroxide etc., it has also become dosage form is eliminated,
It is at home and abroad used less now；The two is main afterwards.
Common tin-stripping wastewater processing method both at home and abroad, comprising:
1, acidic precipitation agent facture
Make heavy metal precipitation by using acidic precipitation agent (acid compound of SH containing sulfydryl such as vessel used to hold grain at the imperial sacrifice S, HSC- etc.), ties therewith
The nitrate anion of conjunction reverts to nitric acid, achievees the purpose that waste liquid recovery is made to move back tin ability.Fe3+ and nitric acid are adjusted to former by regenerated liquid
Again tin is moved back after beginning concentration, however precipitating reagent toxicity added by this technique is bigger, it is difficult to the metallization for operating, and settling
It is big to close object recovery difficult, influences economic benefit, and significant portion tin stripper effective component can be settled, after influencing tin stripper regeneration
Effect.
2, alkaline chemical precipitation method
Sodium hydroxide is added into waste liquid, Kocide SD precipitating is generated, after supernatant further uses ion-exchange copper removal
Discharge, Kocide SD precipitating are recycled.The method has many advantages, such as easy to operate, and equipment investment is few, but micro-corrosion liquid component meets with
To destroy can not reuse have discharge of wastewater, economic benefit and social benefit be not high.
It obtains the precipitating of Kocide SD after acid-base neutralization, after filtration washing, gas washing in SA production industrial cupric sulfate is added.The technique
Simple possible, easy to operate, cost is relatively low, but it is neutralized after, micro-corrosion liquid, which is unable to fully recovering, discharge of wastewater.
3, it is evaporated under reduced pressure absorption method
(73 DEG C or so) are distilled by low-temperature reduced-pressure, the nitric acid distilled out is absorbed with water, forms dilute nitric acid solution, is directly used
It being filtered after the acid supplement of regenerated liquid, tin copper metal ion leading precipitating reagent precipitating, regenerated liquid supplements active principle Recycling,
This simple process is convenient, however the problem is that, the dust technology concentration for being evaporated under reduced pressure out is very low, and recycling increases
The total amount of tin stripper, thus other compositions added by increasing, and added lead precipitating reagent less effective.
The present invention is directed to PCB circuit board industry and carries out moving back tin-stripping wastewater caused by tin process, provides a kind of PCB and moves back
The lossless regeneration and treatment technique of tin waste water.
Summary of the invention
Technical problems based on background technology, the invention proposes a kind of lossless regeneration treatments of PCB tin-stripping wastewater
Technique.
Technical scheme is as follows:
A kind of lossless regeneration and treatment technique of PCB tin-stripping wastewater, comprising the following steps:
Step 1: the spent solder stripper being collected into be carried out to the separation of tin copper first；
Why speed declines waste liquid with activity, is the increase because of the exogenous metal ions in its medical fluid, by it
One of the emphasis implementation steps of this technique are separated into waste liquid.It realizes separation exogenous metal ions, reduces its containing in waste liquid
Amount, the active and molten copper ability for improving tin stripper again is the purpose of tin copper separation.
Its step includes:
The allotment of 1A release agent；
Since release agent solubility is affected by temperature larger, and its property less stable, so first being adjusted before addition
Match, the release agent of 10% concentration of allotment is added in solution, so that contact is more abundant, reacts rapider, more comprehensively.
The addition of 1B tin copper release agent and waste tin stripper；
Waste tin stripper is added while tin copper release agent is added into the collecting vessel for be stored with waste liquid, and side edged starts
(total amount that the amount of release agent is generally less than reacted completely is added) in blender, reacts it sufficiently.
The separating and filtering of 1C sediment；
To accelerate solid-liquor separation speed, and its separation is more comprehensively, and the medical fluid of fully reacting is pumped into filter, keeps it solid
Liquid separation, is reduced the regenerated liquid of tin copper ion, and filtering out the tin copper cake come can be when product sale or reproduction；
Step 2: the concentration of medical fluid；
Since when moving back tin reaction, nitric acid is easy to decompose, when reaching the standard of discharge waste liquid, the concentration of nitric acid is past
Past decreased, the medicament being added when plus the separation of tin copper is liquid, therefore the liquid medicine after having separated tin copper needs slightly
Concentration.Solution after separation is concentrated and separated by distillation, to improve the content of tin stripper, reduces the difficulty of allotment
Degree, improving service efficiency and reducing discharge and maintain the degree of balance of regeneration and production is the main purpose being concentrated.What it was concentrated
Step includes:
2A vacuum distillation；
By reduce tin copper metal ion waste liquid be pumped into economic benefits and social benefits vacuum distillation tower, determine vacuum degree (not less than-
0.05Mpa) for temperature at 65-80 DEG C, distillation stops distillation after the total volume of medical fluid reduces about 3/5 after starting in control tower.
The static cooling of 2B concentrate；
The liquid that 2C is distilled out is collected in together；
Due to being vacuum distillation, the solution steamed is that concentration compares lower dust technology, and separating liquid is added to after collecting
Release agent Allocating Circle uses, and can also be ready for use on stripping and hanging liquid, realizes that 100% uses degree.
Step 3: component is deployed；
Tin regenerated liquid is moved back since its parameter has a certain difference such as concentration of nitric acid, iron content after concentration, is needed to it
Addition reduction ingredient to guarantee that it moves back tin effect, and adjustment period parameters such as copper-protection agent, brightener (BTA, ferric nitrate) is added
As new liquid medicine, each parameter (including acidity, iron concentration etc.) inside concentrate is measured, is calculated according to the result of measurement
The amount for adding reduced ingredient, adds the amount of reduction；
Step 4: separating liquid recycles
After separation is distilled and separates, since it contains part nitric acid, directly drains and do not meet environmental protection and sustainable development
Exhibition, therefore the separating liquid separated is recycled, it is carried out to allotment release agent again or is applied to stripping and hanging liquid
Modulation in, meet 100% recycling principle.
Preferably, in the step one, tin copper release agent cannot add it is excessive so that exist in tin stripper it is excessive and
It influences its regeneration and moves back tin effect, and the amount added can not be very few, so that the still mistake of tin copper content present in waste tin stripper
High same influence regenerates and moves back tin effect, its parameter of different tin-stripping wastewaters is different, therefore having before adding tin copper release agent must
It will be to the measurement of the inside tin copper content, according to the existing amount of tin copper content to add.Additional amount, which has to be lower than, completely reacts
Total amount can guarantee not having residual in liquid medicine in this way, and additional amount can not be too low, to reduce using effect after its regeneration,
If being calculated according to the parameter of waste tin stripper caused by current most of factory, tin concentration 80-100g/L, copper concentration 10-
20g/L, the added amount of remover must not then be lower than 127.5g/L.
Preferably, in the step one, after addition release agent mixing, it is stirred, and the time stirred cannot
It is too short so that reaction not exclusively, can not it is too long so that influence filtering and holding time, destroy component, generally stir when
Between determine between 30min-60min；Same reason, the speed of stirring cannot it is excessively slow so that reaction not exclusively, can not
It is too fast so that influence filtering, destroy component, the revolving speed of stirring is advisable between 100-120r/min.
Preferably, in the step two, when distillation, controls vacuum degree and temperature is the key point of distillation, vacuum
Degree will ensure in -0.05Mpa to distill hereinafter, carrying out distillation first segment temperature with a point three-stage manipulation temperature and determining at 62-67 DEG C
25-35min, second segment vapo(u)rizing temperature determine that, in 68-72 DEG C of distillation 25-35min, third section vapo(u)rizing temperature is determined at 73-77 DEG C
Distill 50-70min.
It is distilled due to passing through, and nitric acid has oxidisability, the additive in tin stripping liquid is generally organic matter, therefore distills
Resolve into C, H, O substantially afterwards, and other substances are heated to volatilize or be oxidized and become other substances.
Technological principle of the invention
1, tin reaction principle is moved back
Sn+4HNO3(dense)=H2SnO3↓+4NO2↑+H2O；
2, waste tin stripper regeneration precipitating principle
2H2C2O4+2H2SnO3=2SnC2O4↓+4H2O+O2↑
H2C2O4+Cu(NO3)2=CuC2O4↓+2HNO3。
The invention has the beneficial effects that: this technique is to be directed to PCB circuit board industry move back caused by tin process
The lossless regeneration and treatment technique of tin-stripping wastewater, the metallic tin copper compound purity that technical process is extract from waste tin stripper
Height is made a silk purse out of a sow's ear, and ensures to move back tin effect after tin stripper regeneration.Its technical process is by the spent solder stripper to failure
Be added it is suitable efficiently separate agent and make copper in spent solder stripper, tin ion keeps moving back by being separated after filtering with tin stripping liquid
The original useful chemical component of tin liquor, then pass through and be concentrated after a series of process flows such as adjustment parameter, so that failure is moved back
Tin water energy enough recirculates utilization, and does not influence it and move back tin effect.This technique is not singly containing simple, at low cost, easy behaviour
The advantages that making, and there are also zero-emission, the economic benefits of 100% recycling.
Detailed description of the invention
Fig. 1: the lossless regeneration and treatment technique flow chart of PCB tin-stripping wastewater of the invention.
Specific embodiment
Embodiment 1:
A kind of lossless regeneration and treatment technique of PCB tin-stripping wastewater, comprising the following steps:
Step 1: the spent solder stripper being collected into be carried out to the separation of tin copper first；
Why speed declines waste liquid with activity, is the increase because of the exogenous metal ions in its medical fluid, by it
One of the emphasis implementation steps of this technique are separated into waste liquid.It realizes separation exogenous metal ions, reduces its containing in waste liquid
Amount, the active and molten copper ability for improving tin stripper again is the purpose of tin copper separation.
Its step includes:
The allotment of 1A release agent；
Since release agent solubility is affected by temperature larger, and its property less stable, so first being adjusted before addition
Match, the release agent of 10% concentration of allotment is added in solution, so that contact is more abundant, reacts rapider, more comprehensively.
The addition of 1B tin copper release agent and waste tin stripper；
Waste tin stripper is added while tin copper release agent is added into the collecting vessel for be stored with waste liquid, and side edged starts
(total amount that the amount of release agent is generally less than reacted completely is added) in blender, reacts it sufficiently.
The separating and filtering of 1C sediment；
To accelerate solid-liquor separation speed, and its separation is more comprehensively, and the medical fluid of fully reacting is pumped into filter, keeps it solid
Liquid separation, is reduced the regenerated liquid of tin copper ion, and filtering out the tin copper cake come can be when product sale or reproduction；
Step 2: the concentration of medical fluid；
Since when moving back tin reaction, nitric acid is easy to decompose, when reaching the standard of discharge waste liquid, the concentration of nitric acid is past
Past decreased, the medicament being added when plus the separation of tin copper is liquid, therefore the liquid medicine after having separated tin copper needs slightly
Concentration.Solution after separation is concentrated and separated by distillation, to improve the content of tin stripper, reduces the difficulty of allotment
Degree, improving service efficiency and reducing discharge and maintain the degree of balance of regeneration and production is the main purpose being concentrated.What it was concentrated
Step includes:
2A vacuum distillation；
By reduce tin copper metal ion waste liquid be pumped into economic benefits and social benefits vacuum distillation tower, determine vacuum degree (not less than-
0.05Mpa) for temperature at 65-80 DEG C, distillation stops distillation after the total volume of medical fluid reduces about 3/5 after starting in control tower.
The static cooling of 2B concentrate；
The liquid that 2C is distilled out is collected in together；
Due to being vacuum distillation, the solution steamed is that concentration compares lower dust technology, and separating liquid is added to after collecting
Release agent Allocating Circle uses, and can also be ready for use on stripping and hanging liquid, realizes that 100% uses degree.
Step 3: component is deployed；
Tin regenerated liquid is moved back since its parameter has a certain difference such as concentration of nitric acid, iron content after concentration, is needed to it
Addition reduction ingredient to guarantee that it moves back tin effect, and adjustment period parameters such as copper-protection agent, brightener (BTA, ferric nitrate) is added
As new liquid medicine, each parameter (including acidity, iron concentration etc.) inside concentrate is measured, is calculated according to the result of measurement
The amount for adding reduced ingredient, adds the amount of reduction；
Step 4: separating liquid recycles
After separation is distilled and separates, since it contains part nitric acid, directly drains and do not meet environmental protection and sustainable development
Exhibition, therefore the separating liquid separated is recycled, it is carried out to allotment release agent again or is applied to stripping and hanging liquid
Modulation in, meet 100% recycling principle.
Table 1 is each parameter in the embodiment of the present invention 1:
It summarizes below to process flow of the invention:
This process flow has the characteristics that following major:
1, it is free from risk, low investment, high repayment；
For this technique due to its process flow maturation, manipulation is simple, and production is easy, and our company's personnel experience is abundant, can be very
Good ensures safety in production, and what client was undertaken is to be free from risk, it is only necessary to provide corresponding place to our company and install equipment, processing
Tin-stripping wastewater not only ensures the supply of tin stripper, also makes a silk purse out of a sow's ear at once.
2, simple process is easy manipulation and continuous and automatic；
The principle and its process of this technique production are all fairly simple, and process operation process is easy manipulation, and employee is easy
It grasps, can all have a corresponding emergency measure for processing emergency event, high degree reduces risk factor.
3, the energy conservation and environmental protection of zero-emission realizes 100% recycling；
Copper and tin precipitating, and utilization tin stripper and the separating liquid of circular regeneration are recycled using lossless separating technology, made
Solution component is able to complete-reclaiming, and recycling line is made to become the clean manufacturing line of zero-emission, and resource utilization reaches 100%,
Ensure to produce high-efficiency environment friendly.
4, occupied area is small, and processing speed is fast, treating capacity is big；
Moon treating capacity designed by this technique is 50 tons/month, and occupied area only needs 80 square metres, effective land productivity
With land resource, and what equipment took is continuous production processing mode, the resource utilization greatly improved.
5, technique does not destroy component, keeps the original effect of tin stripper；
Although this technique is simple, do not destroy, keeps in ingredient of the regenerative process for tin stripper script
The original ingredient of tin stripper, the influential effect of the retrogressing tin regenerated on it is all minimum or does not influence, it can be ensured that client's
Move back tin process excellent effect.
6, technique production and its maintenance cost are low；
For other regenerative systems, this technique is consumed energy well below other again using release agent and destilling tower
Raw system, and the long-range advantage used is produced in process flow, for maintenance due to it is most of be all some to set substantially
It is standby, therefore maintenance difficulties are low, it is at low cost.
7, the quality assurance for the tin stripping liquid additive being recycled；
Due to regenerated difficulty and the influence for moving back the factors such as tin effect, traditional tin stripper falls after being finished with regard to direct emission,
And in continuous regenerative process, requirement of the increase of foreign substance to additive is very high, therefore, for how guaranteeing to produce
The these problems such as quality and permanent circulation and stress, our company carry out a system and in-depth study, investment to tin stripper
A large amount of manpower and material resources are developed specifically for moving back the respective additive of tin, lossless are recycled back to realize the permanent of tin stripper
With, and ensure that and move back the stability and other issues that tin speed moves back tin effect and tin stripper.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (4)
1. a kind of lossless regeneration and treatment technique of PCB tin-stripping wastewater, which comprises the following steps:
Step 1: the spent solder stripper being collected into be carried out to the separation of tin copper first；Its step includes:
The allotment of 1A release agent；
The addition of 1B tin copper release agent and waste tin stripper；
The separating and filtering of 1C sediment；
Step 2: the concentration of medical fluid；It is concentrated the step of include:
2A vacuum distillation；
The waste liquid for reducing tin copper metal ion is pumped into economic benefits and social benefits vacuum distillation tower, determines vacuum degree (not less than -0.05Mpa) control
For temperature at 65-80 DEG C, distillation stops distillation after the total volume of medical fluid reduces about 3/5 after starting in tower processed；
The static cooling of 2B concentrate；
The liquid that 2C is distilled out is collected in together；
Step 3: component is deployed；
Tin regenerated liquid is moved back since its parameter has a certain difference such as concentration of nitric acid, iron content after concentration, needs to be added to it
Reduction ingredient to guarantee that it moves back tin effect, and copper-protection agent, brightener is added, measures each parameter inside concentrate, according to
The result of measurement calculates the amount for adding reduced ingredient, adds the amount of reduction；
Step 4: separating liquid recycles
After separation is distilled and separates, since it contains part nitric acid, directly drains and do not meet environmental protection and sustainable development, because
This recycles the separating liquid separated, it is carried out to allotment release agent or the modulation applied to stripping and hanging liquid again
In.
2. the lossless regeneration and treatment technique of PCB tin-stripping wastewater as described in claim 1, which is characterized in that the step one
In, it is calculated according to tin concentration 80-100g/L, copper concentration 10-20g/L, amount added by remover must not then be lower than 127.5g/L.
3. the lossless regeneration and treatment technique of PCB tin-stripping wastewater as described in claim 1, which is characterized in that the step one
In, after addition release agent mixing, it is stirred, and the time stirred is between 30-60min；The revolving speed of stirring is in 100-
Between 120r/min.
4. the lossless regeneration and treatment technique of PCB tin-stripping wastewater as described in claim 1, which is characterized in that the step two
In, when distillation, vacuum degree will ensure in -0.05Mpa to determine hereinafter, carrying out distillation first segment temperature with a point three-stage manipulation temperature
In 62-67 DEG C of distillation 25-35min, second segment vapo(u)rizing temperature is determined in 68-72 DEG C of distillation 25-35min, third section vapo(u)rizing temperature
It determines in 73-77 DEG C of distillation 50-70min.
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| CN110372028A (en) * | 2019-06-14 | 2019-10-25 | 西陇科学股份有限公司 | A kind of industrialized preparing process of high-purity sulfuric acid silver |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008125728A2 (en) * | 2007-04-13 | 2008-10-23 | Yara Suomi Oy | Method for the treatment and reuse of a stripper solution |
| CN105460972A (en) * | 2015-12-28 | 2016-04-06 | 广州科城环保科技有限公司 | Recycling method of circuit board solder stripping waste liquid |
| CN106186420A (en) * | 2016-08-04 | 2016-12-07 | 深圳市洁驰科技有限公司 | A kind of waste tin stripper processing system and processing method |
-
2018
- 2018-12-25 CN CN201811590568.8A patent/CN109534575A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008125728A2 (en) * | 2007-04-13 | 2008-10-23 | Yara Suomi Oy | Method for the treatment and reuse of a stripper solution |
| CN105460972A (en) * | 2015-12-28 | 2016-04-06 | 广州科城环保科技有限公司 | Recycling method of circuit board solder stripping waste liquid |
| CN106186420A (en) * | 2016-08-04 | 2016-12-07 | 深圳市洁驰科技有限公司 | A kind of waste tin stripper processing system and processing method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110372028A (en) * | 2019-06-14 | 2019-10-25 | 西陇科学股份有限公司 | A kind of industrialized preparing process of high-purity sulfuric acid silver |
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