CN102531280A - Method for treating wastewater of printed circuit board - Google Patents

Method for treating wastewater of printed circuit board Download PDF

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Publication number
CN102531280A
CN102531280A CN2011104281833A CN201110428183A CN102531280A CN 102531280 A CN102531280 A CN 102531280A CN 2011104281833 A CN2011104281833 A CN 2011104281833A CN 201110428183 A CN201110428183 A CN 201110428183A CN 102531280 A CN102531280 A CN 102531280A
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Prior art keywords
solution
value
circuit board
printed circuit
wastewater
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CN2011104281833A
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Chinese (zh)
Inventor
周洋
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SHENZHEN YOULIN ENVIRONMENT PROTECTION CO Ltd
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SHENZHEN YOULIN ENVIRONMENT PROTECTION CO Ltd
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Priority to CN2011104281833A priority Critical patent/CN102531280A/en
Publication of CN102531280A publication Critical patent/CN102531280A/en
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Abstract

The invention discloses a method for treating wastewater of a printed circuit board. The method comprises the following steps: (1) classifying workshop wastewater; (2) pre-processing; (3) separately reacting and depositing; (3) intensively reacting and depositing; (4) adjusting the pH value; (6) biochemically treating; (7) biochemically reacting and depositing; and (8) adjusting the pH value. The method comprises the following specific steps: classifying the wastewater into organic wastewater, comprehensive wastewater and waste acid; respectively pre-processing the organic wastewater, the comprehensive wastewater and the waste acid; adjusting the pH value of the organic wastewater to be 10-11; adding a Ca(OH)2 solution, a Na2S solution, a FeSO4 solution and a PAM (polyacrylamide) solution into a reaction tank in sequence for reaction; then mixing the treated wastewater with the comprehensive wastewater, adjusting the pH value to be 10-11, and adding the Ca(OH)2 solution, the Na2S solution, the FeSO4 solution and the PAM solution into the reaction tank in sequence for reaction; then adjusting the pH value to be 8-9 for biochemically treating; and finally adjusting the pH value to be 7-8.5 for biochemical reaction and precipitation. After the wastewater is treated by the method of the invention, the treated wastewater meets the sewage discharge standard, and contributions are made for environmental protection causes in China.

Description

A kind of method of handling printed circuit board wastewater
Technical field
The present invention relates to a kind of method of handling waste water, especially a kind of method of handling the waste water that produces in the printed circuit board process.
Background technology
Along with developing rapidly of electronic industry, the enterprise that produces PC board become an emerging industry, yet its contaminated wastewater is also more and more serious more and more.Resolving the technical problem of PC board wastewater treatment, also is efforts at environmental protection person's a vital task.
With the insulcrete is the plate that base material is processed into certain size, has a conductive pattern and hole that all design in the above at least, and to realize the electric interconnection between the components and parts, this plate is called printed substrate, is called for short circuit card (PCB), also often is called wiring board.
Printed substrate mainly comprises rigidity and flexible single plate (single sided board and dual platen) and multi-ply wood.The single sided board only one side of a laminate has conductive pattern; Dual platen is that the two sides all has figure; Multi-ply wood forms an integral body by a plurality of alternative conductive patterns and insulation material layer after heating and pressurizing is carried out lamination; The number of plies is more than two-layer, and its manufacture craft is in that to be laminated into a whole back roughly the same with the manufacture craft of single plate.
Single-clad board generally adopts the paper phenol matrix copper-clad laminate to process, and is mainly used in product for civilian use Source Music, televisor, electronic instrument etc.More double-sided printed-circuit board adopts epoxy glass fabric to cover Copper Foil and processes, and is mainly used in the higher communication electronics of performance requriements, high grade instrument and meter and electrometer computingmachine etc.
The epoxy glass fabric copper coated foil plate is generally adopted in the manufacturing of multilayer printed circuit board; Earlier make the inner conductor figure, then according to design requirements, several inner conductor graphics overlays with the Copper Foil etching method; Be placed in the special-purpose laminating machine; Through hot pressing, sticking and operation, process veneer sheet with inner conductor figure, later manufacturing procedure and above-mentioned single sided board are basic identical.
Because circuit card is more and more meticulousr small, so working accuracy improves day by day, causes PCB Production to become increasingly complex.Its production process has tens procedures, and the per pass operation all has chemical substance to produce waste water, and the pollutent that printed circuit board produces in process of production is following:
One, copper: owing to being removes unnecessary copper to stay circuit in copper-clad plate, so copper is topmost pollutent in the Printed Circuit Board Design waste water, and Copper Foil is a main source.In addition, because the circuit of dual platen, each layer of multi-ply wood needs conducting, boring and copper facing on substrate; Make each layer circuit turn-on; And in last first floor copper facing of base material (being generally resin) and pilot process, also have electroless copper, electroless copper to adopt complex copper, with the copper sedimentation velocity and the copper deposit thickness of control stabilization; The general EDTA-Cu (cupric ethylene diamine tetraacetate sodium) that adopts also has other compositions.
Also contain complex copper behind the electroless copper in the rinse water of printed board.In addition, also have nickel plating, gold-plated and zinc-plated lead in the PCB Production, therefore also contain these heavy metals.
Two, organism: in making operations such as circuitous pattern, Copper Foil etching, circuit welding; Use printing ink that the Copper Foil that needs protection is partly covered; It is returned willingly again after finishing, and these processes produce the organism of high density, and the COD that has (COD) is up to 10～20g/L.These high-concentration waste waters account for about 5% of Total Water greatly, also are the main sources of PCB Production chemical oxygen demand of waste water (COD).
Three, ammonia nitrogen: different according to production process, the technology that has contains ammoniacal liquor and ammonium chloride etc. in etching solution, and they are main sources of ammonia nitrogen.
Except above major pollution thing, also have acid, alkali, nickel, lead, tin, manganese, cyanide ion and fluorine.In the PCB Production process, use sulfuric acid, hydrochloric acid, nitric acid and sodium hydroxide are arranged; And tens kinds of various soups such as etching solution, chemical plating fluid, electroplate liquid, activation solution, presoaks etc.; Composition is numerous and diverse; Except most of composition is known, also have on a small quantity not principal component, this makes wastewater treatment complicated and difficult more.
Traditional method of wastewater treatment of printed circuit board (PCB) has several very big defectives:
One of which: some producer is with wastewater collection Unified Treatment together, and the technology of the said printed circuit board (PCB) of front is much very complicated, and the pharmaceutical chemicals character of its use also is that each is different, and the mixing of blindness will be grown new pollutent like this.
Its two: it is very thin that some producer considers that the waste water on this production technique of naming a person for a particular job divides, and accomplishes a technology one processing, like this will be very complicated in operation.At first be the very complicacy that the workshop divides the pipeline of water to walk, also very complicated in the configuration of sewage treatment equipment then, on economic benefit, lose more than gain like this.
Its three: traditional technology generally adopts the materialization precipitator method; Usually general materialization intermediate processing is limited to the removal effect of COD (COD); And the COD of printing ink wastewater (COD) is diluted even if pass through usually all than higher, and COD (COD) also usually can exceed standard.
Summary of the invention
For addressing the above problem, the technical problem that the present invention will solve provides a kind of method of handling the waste water that produces in the printed circuit board process.
To achieve these goals, the technical scheme of the present invention's employing is that a kind of method of handling printed circuit board wastewater may further comprise the steps:
(1) workshop classification of waste;
(2) pre-treatment;
(3) separate reaction precipitation;
(4) concentrate reaction precipitation;
(5) adjustment pH value;
(6) biochemical treatment;
(7) biochemical reaction deposition;
(8) adjustment pH value.
Preferably, waste water is divided into three types in organic waste water, comprehensive wastewater and spent acid in the said step (1).
Preferably, pre-treatment may further comprise the steps in the said step (2):
A. organic waste water is after equalizing tank is regulated, and getting into pH value is the acid out pond acid out of 2-3, separates out the film slag, and waste water filters through pressure filter;
B. comprehensive wastewater is in harmonious proportion through simple soda acid, directly gets into to concentrate reaction precipitation;
C. spent acid is squeezed in the middle acid out pond of step (a).
Preferably, in the said step (3) pH value in the reaction tank transferred to 10-11 after, in reaction tank, add Ca (OH) successively 2Solution, Na 2S solution, FeSO 4With PAM solution.
Preferably, in the said step (4) pH value in the reaction tank transferred to 10-11 after, in reaction tank, add Ca (OH) successively 2Solution, Na 2S solution, FeSO 4Solution and PAM solution.
Preferably, pH value is 8-9 in the said step (5).
Preferably, adopt the treatment process of A/O in the said step (6): the oxygen and aerobic of holding concurrently.
Preferably, in the said step (8) pH value in the reaction tank is transferred to 7-8.5.
Preferably, reaction precipitation is a two-stage or multistage in the said step (4).
Preferably, in said step (3), (4), (5), (6), (7), materialization deposition, sulfide washing out method combine with biochemical treatment process.
The invention has the beneficial effects as follows; Participate in the effluent segregation work of board production before the waste water treatment engineering design, and examine the chemical agent composition of per pass operation item by item, guaranteed the accuracy and the thoroughness of effluent segregation like this from the source with the production technology personnel; For subsequent disposal waste water is accomplished fluently solid basis; After commissioning device was stable, daily operational management was simpler and easy, aspect working cost than additive method economy many; Reach cut the waste, rationally utilize, purpose steady in a long-term up to standard, for the Environmental Protection in China cause is contributed.
Embodiment
According to the difference of each Workshop Production technology, the waste water of its generation is also different, to the detection of each process section water quality; Because the medicament that each technology is added is different; But the composition of each medicament is marked before in interpolation, the detection here just just detects its concentration, is stained with a little waste liquid with the test strip of corresponding pollutent; With reading general concentration numbers after the colorimetric card colorimetric; Thereby, be divided into three kinds to waste water, that is: organic waste water, comprehensive wastewater and spent acid according to principal pollutant contained in the waste water.
Organic waste water be COD (COD) content than higher waste water, before getting into reaction precipitation, to carry out pre-treatment earlier.The organic waste water that shunting is collected is introduced the acid out pond, the pH value in acid out pond is added acid transfer to 2.5, separate out a large amount of film slags of dissolved in the organic waste water, after the pressure filter press filtration, filtered water is to subsequent disposal.
Comprehensive wastewater is the higher waste water of heavy metal ion content, directly gets into after being in harmonious proportion through simple soda acid and concentrates reaction precipitation.
Spent acid is the lower waste water of pH value, as a part of acid source in organic waste water acid out pond.
Through the organic waste water after the acid out, get into the first step and separate reaction precipitation, mainly be to remove a small amount of heavy metal ion that organic waste water contains.Add Ca (OH) 2 solution after at first the waste water pH value in the reaction tank being transferred to 10-11, add Na2S solution then, then add FeSO4 solution, add PAM solution at last.
When pH value below 10, heavy metal ions in wastewater can not get enough OH -Left and formed precipitation of hydroxide with it; PH value is more than 11, makes OH on the contrary -Left surplus.
A ++OH -＝AOH
And under alkaline condition, S2 can not form H2S gas in the Na2S solution, forms sulfide precipitation with heavy metal.
A 2++S 2-＝AS
After the reaction, add under the effect of dissolving of coagulating agent FeSO4 solution and hydrolysate, make that dispersive heavy metal precipitation thing and other colloid are focused into bigger coagulum in the organic waste water.
Fe 2++e -＝Fe 3+
In reaction tank, add the PAM aqueous solution at last, the PAM aqueous solution is water miscible chain high molecular polymer.Through its molecular force effect colloid in the waste water or tiny suspended substance are attached together; These particulates are put up a bridge through the chain polymer of the PAM aqueous solution and are coupled to flock one by one; Increase its proportion, make colloid, suspended substance, the throw out sedimentation fast that forms in the waste water.
Waste water gets into the tube settling sedimentation through after the above-mentioned reaction.
Comprehensive wastewater through after the simple adjustment also will pass through reaction precipitation.But at the reaction precipitation of comprehensive wastewater should be twice or repeatedly.
Because heavy metal ion contained in the comprehensive wastewater is compared organic waste water, high a lot.So general reaction precipitation once is not reach treatment effect far away.Have the people and say, you can heighten pH value, and medicament adds just impassable more.But the flow velocity of waste water is than faster, particularly in the bigger factory of some water yields.Medicament have little time at all with water in pollutent interact, so the excessive treatment effect that not only do not reach of the amount that medicament adds can cause secondary pollution on the contrary.Can cause irreversible injury to follow-up biochemical treatment system like this.
Last concentrated reaction precipitation, the organic waste water that will pass through after the previous processed mixes with comprehensive wastewater, adds Ca (OH) after once more the waste water pH value in the reaction tank being transferred to 10-11 2Solution adds Na then 2S solution then adds FeSO 4Solution adds PAM solution at last through the one or many reaction precipitation.Purpose is to dilute each other pollutent contained among the other side, and through the processing in early stage, heavy metal has reached emission standard.Though two strands of water are through mix, COD (COD) has certain decline, and just handled heavy metal emphatically early stage, but COD (COD) content is still very high, and follow-up treatment process will carry out single-minded processing with regard to COD (COD).
Before getting into biochemical treatment system, adjust water ph value.Be stained with a little waste liquid with the PH test paper; Color according to color is corresponding with colorimetric card is confirmed pH value; Add acid or alkali is adjusted to the pH value scope 8-9 that biochemical treatment system can be accepted according to the height of pH value, this scope is the needed reasonable range of biochemical system mikrobe.
Biochemical treatment is to adopt the A/O pattern.A/O can be that anaerobic and aerobic cooperate, and also can be hold concurrently oxygen and aerobic cooperation, and that present embodiment adopts is the latter.Anaerobism is difficult to guarantee the content of its dissolved oxygen (DO) under very big situation, and its gas hazardous through being produced after the biochemical reaction; And the oxygen of holding concurrently is better than anaerobism to a great extent; At first be that desired interval is wider on the concentration of dissolved oxygen (DO); Can well go control; And its reaction unit is more unlimited, and some gases of being produced of reaction will soon dissipate, and hold concurrently oxygen bacterium and aerobic bacteria utilize self metabolism that the larger molecular organics in the waste water is converted into CO2, H2O and mineral compound.
Carry out biochemical reaction deposition to above-mentioned reacted waste liquid then, because the waste water after handling is precipitate this to biochemical reaction LZT, the pollutent in its water is up to standard basically; This reaction is exactly to remove suspended substance and the microbial population that contains in the water.Mainly be in reaction tank, to add Poly aluminum Chloride (PAC) (PAC) solution, make these short grained suspended substances and microbial population form big flocculence object, add SEPIGEL 305 (PAM) solution afterwards again and make its deposition, form mud.The mud here is the preferably backflow point that mud refluxes.
Because through the waste liquid after the biochemical reaction precipitation process; PH value slowly is reduced to about 6-7 by original 8-9, sometimes even can be lower, exceeds the discharging scope in order to prevent last water quality pH value; Need before discharging, carry out a PH adjustment; Be stained with a little waste liquid with the PH test paper, confirm pH value, when pH value is higher than 9, in waste liquid, add an amount of acid solution according to the color that color is corresponding with colorimetric card; When pH value is lower than 6, in waste liquid, add an amount of alkaline solution, the waste liquid pH value of discharge is remained between the 7-8.5.
In above-mentioned institute responded, the method that has adopted materialization deposition, sulfide washing out method to combine with biochemical treatment process was handled waste water.
Only be preferred implementation of the present invention in sum, should be understood that for the person of ordinary skill of the art that under the prerequisite that does not break away from the present invention's design, can also make several distortion and improvement, these also should be regarded as within protection scope of the present invention.

Claims (10)

1. a method of handling printed circuit board wastewater is characterized in that, may further comprise the steps:
(1) workshop classification of waste;
(2) pre-treatment;
(3) separate reaction precipitation;
(4) concentrate reaction precipitation;
(5) adjustment pH value;
(6) biochemical treatment;
(7) biochemical reaction deposition;
(8) adjustment pH value.
2. a kind of method of handling printed circuit board wastewater according to claim 1 is characterized in that, waste water is divided into three types in organic waste water, comprehensive wastewater and spent acid in the said step (1).
3. a kind of method of handling printed circuit board wastewater according to claim 1 is characterized in that, pre-treatment may further comprise the steps in the said step (2):
A. organic waste water is after equalizing tank is regulated, and getting into pH value is the acid out pond acid out of 2-3, separates out the film slag, and waste water filters through pressure filter;
B. comprehensive wastewater is in harmonious proportion through simple soda acid, directly gets into to concentrate reaction precipitation;
C. spent acid is squeezed in the middle acid out pond of step (a).
4. a kind of method of handling printed circuit board wastewater according to claim 1 is characterized in that, in the said step (3) pH value in the reaction tank transferred to 10-11 after, in reaction tank, add Ca (OH) successively 2Solution, Na 2S solution, FeSO 4Solution and PAM solution.
5. a kind of method of handling printed circuit board wastewater according to claim 1 is characterized in that, in the said step (4) pH value in the reaction tank transferred to 10-11 after, in reaction tank, add Ca (OH) successively 2Solution, Na 2S solution, FeSO 4Solution and PAM solution.
6. a kind of method of handling printed circuit board wastewater according to claim 1 is characterized in that, pH value is 8-9 in the said step (5).
7. a kind of method of handling printed circuit board wastewater according to claim 1 is characterized in that, adopts the treatment process of A/O in the said step (6): the oxygen and aerobic of holding concurrently.
8. a kind of method of handling printed circuit board wastewater according to claim 1 is characterized in that said step transfers to 7-8.5 with the pH value in the reaction tank in (8).
9. according to claim 1 or 5 described a kind of methods of handling printed circuit board wastewater, it is characterized in that reaction precipitation is a two-stage or multistage in the said step (4).
10. a kind of method of handling printed circuit board wastewater according to claim 1 is characterized in that, in said step (3), (4), (5), (6), (7), materialization deposition, sulfide washing out method combine with biochemical treatment process.
CN2011104281833A 2011-12-16 2011-12-16 Method for treating wastewater of printed circuit board Pending CN102531280A (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103304059A (en) * 2013-06-30 2013-09-18 金川集团股份有限公司 System and method for treating acidic wastewater in metallurgical off-gas acid-making process
CN104028536A (en) * 2014-05-27 2014-09-10 上海展华电子有限公司 Waste reducing system and method
CN104418414A (en) * 2013-08-21 2015-03-18 欣兴电子股份有限公司 Waste liquid processing method, waste liquid processing system and equipment thereof
CN104909485A (en) * 2014-03-10 2015-09-16 青岛大学 Printing ink waste liquid treatment and sludge dewatering method
CN106746011A (en) * 2016-12-30 2017-05-31 四川师范大学 The processing method of heavy metal-containing waste water
CN108975533A (en) * 2018-07-20 2018-12-11 江苏吉星新材料有限公司 A kind of Sapphire Substrate intellectualization of factories sewage water treatment method
CN110510776A (en) * 2019-09-04 2019-11-29 中国地质科学院水文地质环境地质研究所 A kind of heavy metal-polluted method for treating water
CN115057593A (en) * 2022-08-03 2022-09-16 广东水清环境治理有限公司 Combined treatment method for circuit board wastewater
CN115259463A (en) * 2022-08-05 2022-11-01 广东水清环保科技有限公司 Pretreatment method of PCB (printed Circuit Board) comprehensive wastewater

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103304059A (en) * 2013-06-30 2013-09-18 金川集团股份有限公司 System and method for treating acidic wastewater in metallurgical off-gas acid-making process
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CN108975533A (en) * 2018-07-20 2018-12-11 江苏吉星新材料有限公司 A kind of Sapphire Substrate intellectualization of factories sewage water treatment method
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CN110510776B (en) * 2019-09-04 2022-03-22 中国地质科学院水文地质环境地质研究所 Heavy metal sewage treatment method
CN115057593A (en) * 2022-08-03 2022-09-16 广东水清环境治理有限公司 Combined treatment method for circuit board wastewater
CN115259463A (en) * 2022-08-05 2022-11-01 广东水清环保科技有限公司 Pretreatment method of PCB (printed Circuit Board) comprehensive wastewater

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Application publication date: 20120704