CN101054247A - Integrated processing technique for waste water in breadboard production - Google Patents
Integrated processing technique for waste water in breadboard production Download PDFInfo
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- CN101054247A CN101054247A CN 200710074651 CN200710074651A CN101054247A CN 101054247 A CN101054247 A CN 101054247A CN 200710074651 CN200710074651 CN 200710074651 CN 200710074651 A CN200710074651 A CN 200710074651A CN 101054247 A CN101054247 A CN 101054247A
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Abstract
The invention relates to an efficient process technology for processing plenty of waste water generated in circuit board production, in particular to a pretreatment technology of high copper waste water and difficult biochemical degradation waste water with high COD in the process technology and entire waste water processing technology. First, sorting waste water reasonably according to nature thereof, dividing into as gold thread cyanogen waste water, nickel waste water, silver waste water, copper waste water, peel ink development waste water, high COD waste water and general aqueous washing water, collecting and specially processing the seven kinds of waste water independently, which key technology is the pretreatment technology for copper waste water, peel ink development waste water and high COD waste water. For copper, the key of waste water processing lies in to break complex compound and prevent secondary complexation of remnant Cu2+ and EDTA when adjusting pH to alkaline value; the key of peeling ink development waste water and high COD waste water lies in the foundation that carries out electrocatalysis oxidize to remove partial CODs, on with raise BOD/COD ratio thereof to improve biochemicalness radically.
Description
Technical field
The present invention relates to a kind of environment-protection wastewater treatment process, in particularly a kind of wiring board production process at classification of waste, high Cu
2+The crucial treatment process of waste water and high density bio-refractory organic waste water.
Background technology
Along with the fast development of electronic product production industry, output and scale that wiring board is produced are increasing, and the wastewater discharge of wherein big-and-middle-sized professional production factory is greatly about 1000T/D～20000T/D.These class waste water principal pollutant are with Cu
2+Be master's the heavy metal ion and the organism (BOD/COD＜10%) of bio-refractory, and Cu
2+Because of the existence of EDTA a large amount of in the waste water (ethylenediamine tetraacetic acid (EDTA)) etc. and be to exist with complex form, chemical stability is very high, is different from general electroplating wastewater fully.Many wiring boards factory is Cu for a long time
2+With COD can not stably reaching standard discharging and perplexing, it is so much that the treatment project standard of this respect and thematic treatise can not show a candle to electroplating wastewater processing.
The waste water that the production of wiring board is discharged from different operation has kind more than 30, and chemical ingredients is very complicated, and wherein copper is waste water because the existence of EDTA (ethylenediamine tetraacetic acid (EDTA)) etc., Cu are arranged
2+Form with complex compound exists; Shelling black waste water and other high-COD waste waters all is the difficult biochemical organic waste water of high density.Also exist other various wastewater such as gold-plated, nickel system simultaneously.Here it is, and board wastewater is different from the feature of electroplating wastewater.
According to (DB4426-1998) first discharge standard of People's Republic of China's " integrated wastewater discharge standard ": PH is between 6-9; COD≤100mg/l; SS≤20mg/l; Cu
2+≤ 0.5mg/l; Pb≤0.5mg/l; Grease≤10mg/l; Colourity≤40 times.Obviously find out from emission standard: the leading indicator of wiring board factory effluent water outlet is Cu
2+And COD.How controlling this index is the major technique key.
Different according to kind of producing wiring board and production technique, the waste water that is produced roughly can be divided into seven kinds: gold-plated line waste water (cyanide wastewater), nickel are that waste water, silver are that waste water, copper are waste water (containing potassium permanganate), stripping ink developer waste water, high-COD waste water (brown melanism waste liquid, Peng Song agent waste water, spray tin first road washing water etc.) and generally wash water.It is up to standard that copper removal is waste water and stripping ink developer waste water, high-COD waste water (brown melanism waste liquid, Peng Song agent waste water, spray tin first road washing water etc.) four kinds of waste water in addition can adopt the comprehensive treating process of commonly industrial wastewater to handle.For stripping ink developer water, brown melanism waste liquid, Peng Song agent waste water, the contour COD waste water of spray tin first road washing water, the COD value is generally at 6000-10000mg/l, though this strand water is proportion about 10% in the whole waste water of wiring board, but it is dense, and the ratio of BOD/COD belongs to the organic waste water of bio-refractory less than 10%.Can adopt the inventor's Chinese patent 00134787.X at the organic waste water of the high COD bio-refractory of this strand, theme as " a kind of high-density organic waste water incapable of degrading biochemically treatment process and device thereof " and do pre-treatment, effectively reduce the COD value, and lifting BOD/COD ratio, improve its biodegradability, follow-up conventional comprehensive treating process is proved effective.
Summary of the invention
Purpose of the present invention provides the treatment process of the waste water that produces in a kind of effective processing circuitry board production technology, and particularly classification, the high-copper at waste water in this technological process is the pretreatment technology and the whole waste water treatment process of waste water and high COD bio-refractory waste water technology.
Purpose of the present invention can reach by following measure:
The treatment process of this complete wiring board factory effluent, characteristics according to the wiring board production technique, can be divided into gold-plated line cyanogen with the character of waste water is that waste water, nickel are that waste water, silver are that waste water, copper are waste water, stripping ink developer waste water, high-COD waste water and generally wash water, above-mentioned seven kinds of waste water are collected separately, handled especially, and its concrete treatment process is as follows:
(1), to collect nickel be waste water, this waste water is a pollutant, national regulation must individual curing, adds in reaction tank and removes the nickel agent, by (the Ni≤1mg/l) of qualified discharge behind the coagulating sedimentation;
(2), to collect silver be waste water, this waste water is a pollutant, national regulation must individual curing, by (the Ag≤0.5mg/l) of qualified discharge behind the coagulating sedimentation;
(3), to collect cyanogen be waste water, though this waste water is not a pollutant, toxicity is very big, also must individual curing up to standard (behind the CN≤0.5mg/l) can with other water combination treatment, avoid diluting suspicion up to standard.Remove through NaClO under the alkaline condition respectively that NaClO removes cyanogen under cyanogen and the acidic conditions, again by behind the catalytic oxidation degree of depth broken cyanide with general washing water combination treatment;
(4), collect stripping ink developer waste water, after an acidifying, enter the catalytic oxidation pond and handle the back coagulating sedimentation, enter pump well after regulating pH value;
(5), collect high-COD waste water, handle through the catalytic oxidation pond, regulate pH value and mix by the pump well that enters behind the coagulating sedimentation in (4) step;
(6), the waste water in the pump well in (5) step is sterilized after secondary sedimentation, then with general washing water combination treatment through the routine biochemistry pond;
(7), to collect copper be waste water, through overregulating pH value and reduction-replacement process, transferring pH value by hydro-oxidation sodium and calcium hydroxide again is about 9, behind the last coagulating sedimentation with general washing water combination treatment;
(8), the water after the processing of (3) (6) (7) is mixed with general washing water, get final product qualified discharge through conventional wastewater treatment process again, promptly enter clean water basin by reduction-displacement, accent PH coagulating sedimentation, sand filtration, PH terminal after regulating, a part is back to production, other qualified discharge.
Purpose of the present invention can also reach by following measure:
The pH value of described (3) step neutral and alkali condition is about 10.
The pH value of acidic conditions is about 4 in described (3) step.
Acidifying for the first time is to adopt H in described (4) step
2SO
4Acidifying equals about 4 pH value.
Regulate about pH value to 7 behind the coagulating sedimentation in described (4) step.
Handle the back through the catalytic oxidation pond in described (5) step and regulate about pH value to 8.5, adopt PAC, PAM coagulating sedimentation.
Regulate pH value and reduction process in described (7) step for using H
2SO
4Regulate the complex compound that makes copper about pH value to 4 and destroy, add FeSO again
47H
2O makes Cu
2+Reduction.
The reaction precipitation process makes about pH value to 9 for adopting adding NaOH in described (7) step, adds Ca (OH) again
2, PAC, PAM, Na
2The S coagulating sedimentation.
Wiring board production wastewater treatment process mechanism is analyzed:
(1) (2) (3) step is well-known treatment process in the technological process;
The organic waste water catalytic oxidation process mechanism of (4) (5) step middle and high concentration bio-refractory is as follows:
The catalytic oxidation principle:
The oxygen in water molecule obtains electronics in the low voltage electric field, form O
2 -The oxyradical ion.Under the catalytic condition, water body produces H
2O
2, and induce hydroxyl radical free radical ion OH simultaneously.Make the partial organic substances mineralising become CO
2And H
2O, the chain rupture of residual organic substances macromole becomes small molecules (hydrolysis), and is oxidized to lipid acid (acidifying) simultaneously.At this moment, BOD/COD will promote significantly, and for subsequently anaerobic and aerobic lay the foundation, otherwise biochemistry can not or be difficult to carry out.
Whole catalyzed oxidation mechanism is as follows:
1) hydrogen peroxide H
2O
2Generation
The O that the outside provides
2Capture the electronics that external electric field provides, form oxyradical ion O
2 -, after series reaction generates H
2O
2
O
2+e
-→O
2 - (1)
H
2O→H
++OH
- (2)
O
2 -+H
+→·O
2H (3)
2·O
2H→O
2+H
2O
2 (4)
Simultaneously
·O
2H+O
2 -→O
2+HO
2 - (5)
HO
2 -+H
+→H
2O
2 (6)
2) generation of hydroxyl radical free radical OH
H
2O
2+e
-→OH
-+·OH (7)
While H
2O
2+ M
2+→ M
3++ OH
-+ OH (8)
M
2++·OH→M
3++OH
- (9)
H
2O
2+M
3+→M
2++H
++·O
2H (10)
H
2O
2+·O
2H→O
2+H
2O+·OH (11)
3) organic mineralising
R+·OH→H
2O+R· (12)
R·+M
3+→R
++M
2+ (13)
R
++O
2→ROO
+→……→CO
2↑+H
2O?(14)
Annotate: R is organic molecule, and M is the catalyst metal atom.
Cu in (7) step
2+Be that waste water treatment process mechanism is as follows:
1) Cu
2+It is the waste water treatment process program
Cu
2+Be waste water in wiring board is produced mainly from potassium permanganate waste water, chemical copper waste water is changed the production process of copper microetch washing water.Major ingredient in the waste water: Cu
2+, EDTA, CuY
2-, KMnO
4, secondly also have HCHO (formaldehyde).
Process flow diagram is represented as follows:
Cu
2+It is the wastewater collection pond
↓
H
2SO
4---adjust PH=4, make complex compound CuY
2-Unstability discharges Cu
2+
↓ finish contact break
FeSO
4
——
☆ KMnO
4FeSO
4Be substituting agent, make Fe
2+Replace CuY
2-In Cu
2+Simultaneously
KMnO in the ↓ waste water
4Also be oxygenant, unnecessary Fe
2+Be oxidized to Fe
3+
NaOH
——
Ca (OH)
2After transferring PH＞9, continue to finish CuY under the meta-alkalescence condition
2-Contact break, alkalescence
CaY under the condition
2-Compare FeY
2-And CuY
2-More stable, produce Cu (OH)
2,
↓ Fe (OH)
2And Fe (OH)
3Catch precipitation altogether
NaOH
——
☆ HCHO produces more Cu (OH) behind PH＞9
2, Fe (OH)
2And Fe (OH)
3
↓ catch precipitation altogether
PAC, PAM---coagulating sedimentation
↓
Na
2S---handle residual micro Cu
2+
↓
Entering comprehensive pond mixes with washing water
↓ comprehensive treating process
↓
Qualified discharge
Annotate: ☆ represents the material that exists in the waste water.
2) chemism
2.1) contact break and displacement under the acidic conditions
Add H
2SO
4Make that PH is about 4, Cu in the waste water
2+With the complex compound loss of stability that EDTA generates, Cu in the waste water
2+, CuY
2-, EDTA is simultaneous,
Cu
2++H
2Y
2-CuY
2-+2H
+
Add FeSO
4After, will make Fe
2+Displacement Cu
2+PH＜5 o'clock, FeY
2-Stability constant greater than CuY
2-Stability constant, that is Fe
2+Compare Cu with the EDTA generation
2+With the more stable complex compound of EDTA, this just finishes contact break and metathetical whole process under the acidic conditions.Reaction formula is as follows:
Fe
2++CuY
2-→FeY
2-+Cu
2+
2.2) KMnO in the waste water
4Removal
KMnO
4Be oxygenant, Fe
2+Be oxidized to Fe
3+
Fe
2++MnO
4 -→Fe
3++MnO
4 2-
Under the acidic conditions, MnO
4 2-Disproportionation easily takes place
3MnO
4 2-+4H
+→MnO
2↓+2MnO
4 -+2H
2O
Above-mentioned two reactions hocket Fe
3+With OH
-Form Fe (OH)
3, and Fe (OH)
3With MnO
2Be that chemical property is more stable, entire reaction will be Fe
2+To Fe
3+Direction moves, and is not a undying circulation.Fe (OH)
3Help the effect of coagulating, impel Cu (OH)
2, Fe (OH)
2With Fe (OH)
3Catch precipitation and water sepn altogether.
And, MnO
4 -Can reduce under the acidic conditions,
MnO
4 -+8H
++5e
-→Mn
2++4H
2O
Under the neutrallty condition, also following reaction can take place
MnO
4 -+2H
2O+3e
-→MnO
2↓+4OH
-
And
Mn
2++2OH
-→Mn(OH)
2↓
Mn (OH)
2Be white depositions, chemically unstable
2Mn (OH)
2+ O
2(oxygen in water) → 2H
2MnO
2
After the neutralization reaction
H
2MnO
2+Mn(OH)
2→2H
2O+MnMnO
2↓
Mn (OH)
2End reaction is generated MnO
2Precipitation.
2.3) Cu (OH) under the alkaline condition
2Formation and stop the secondary complexing
Add Ca (OH)
2With NaOH solution, transfer PH＞9
Under the alkaline condition
Cu
2++2OH
-→Cu(OH)
2↓
Finish Cu
2+Form Cu (OH)
2Precipitation process.Ca (OH) wherein
2Adding, the CaY that alkaline condition generates down
2-Stability constant is greater than CuY
2-And FeY
2-, remaining CuY
2-With major part by Ca
2+Displacement generates more stable CaY
2-
Simultaneously, the extremely strong reductive action of HCHO under the alkaline condition makes Cu (OH)
2Be reduced to Cu
2O.
HCHO+4Cu(OH)
2→CO
2↑+2Cu
2O↓+5H
2O
Ca
2++CO
3 2-→CaCO
3↓
Find out that thus HCHO in the wiring board factory effluent (formaldehyde) also is removed simultaneously.
2.4) Na
2The effect of S
In brown and the melanism waste water, contain NaClO, H
2O
2, Ammonia etc.Add FeSO
4, NaOH and Ca (OH)
2After the pre-treatment, add Na again
2Behind the S
Ni
2++2OH
-→Ni(OH)
2↓
H
2O
2+ClO
-→H
2O+O
2↑+Cl
[Cu(NH
3)
4]
2++Na
2S→CuS↓+2Na
++4NH
3↑
But must note Na
2The calculating of S dosage and control, otherwise H is arranged
2The S gas evolution water surface, and water outlet sulfide exceeds standard.
Water after the processing enters comprehensive pond and mixes comprehensive treating process again and reuse of sand filtration rear section and discharging with washing water.
The present invention has the following advantages:
This technological principle is clear, complete, treatment effect Cu
2+＜0.5mg/l (generally about 0.2mg/l), COD＜100mg/l (generally at 60-80mg/l) is very stable.
Description of drawings
The wiring board production wastewater treatment technical process that Fig. 1 the present invention is complete is always schemed.
Embodiment
The present invention will be described in further detail below in conjunction with the accompanying drawings:
Characteristics according to the wiring board production technique, can be divided into gold-plated line cyanogen with the character of waste water is that waste water, nickel are that waste water, copper are that waste water, stripping ink developer waste water, high-COD waste water, silver are waste water and generally wash water, above-mentioned seven kinds of waste water are collected separately and special the processing, and its concrete treatment process is as follows:
Nickel is waste water through collecting, and adds and removes after the nickel agent carries out chemical coagulation and precipitation, can be effectively the concentration of nickel be controlled at below the 1.0mg/l, can directly drain into the discharge outlet discharging.
Silver is waste water through collecting, and adds NaOH and regulates about pH value to 9, adds PAC, PAM, Na again
2After several medicaments of S carry out chemical coagulation and precipitation, can be effectively the concentration of silver be controlled at below the 0.5mg/l, drains into the discharge outlet discharging.
Cyanogen is waste water principal pollutant prussiates, regulates about pH value to 10 through a NaOH, adds NaClO oxidation broken cyanide, again through a H
2SO
4Regulate about pH value to 4, add NaClO oxidation broken cyanide, then from flowing into catalytic oxidation pond reoxidation broken cyanide, guarantee to flow automatically after cyanogen is below 0.5mg/l the comprehensive adjustment pond with generally wash the water combination treatment.
High COD water system waste water is bio-refractory organic waste water, must add NaOH again and regulate about pH value to 8.5 after catalytic oxidation be handled, and adds PAC, PAM and carries out the coagulating sedimentation processing, improves its biodegradability, enters the pending subsequent disposal of pump well then.
The wastewater collection of stripping ink developer rises to acidification pool to equalizing tank through pump in batches, uses H
2SO
4Regulate about pH value to 4, solid-liquid separation behind the acidification reaction, mud is collected separately, supernatant liquor flows automatically to behind the middle transition pond to squeeze into pump and carries out catalytic oxidation in the catalytic oxidation pond, coagulating waste water precipitation after the oxidation, supernatant liquor rises to biochemistry pool by pump again from flowing into above-mentioned pump well, flow automatically to second pond and sterilization pool (considering water reuse sterilization) then successively, last waste water flows automatically to the comprehensive adjustment pond and handles with the mixing of general washing water.
Copper is that waste water is collected separately, at reduction pond H
2SO
4Regulate about pH value to 4, add FeSO then
47H
2O finishes contact break and displacement whole process, adds NaOH through reaction tank then and regulates about pH value to 9, adds Ca (OH)
2, PAC, PAM, Na
2S reacts coagulating sedimentation, afterwards from flowing into comprehensive adjustment pond and general washing water combination treatment.
General washing waste water and pretreated other waste water of process are collected in the comprehensive adjustment pond by the independent pipeline of collecting separately, still there is the complex compound of a spot of copper and EDTA etc. to exist in the composite waste, therefore lift pump is promoted to water in the reduction pond from the comprehensive adjustment pond, adds H
2SO
4Regulate about pH value to 4, add FeSO
47H
2O further reduces Cu
2+After, finish contact break and displacement whole process, add NaOH and regulate about pH value to 9, add Ca (OH) again
2, PAC, PAM, Na
2S is to Cu
2+Net is caught co-precipitation.Sand tower is set after the precipitated outlet water, and the waste water after the filtration is adjusted the pond at PH and is regulated PH between 6～9, produces all the other dischargings after clean water basin partly are back to.
More than be exactly the process of improving of the wastewater treatment of a complete wiring board factory, if management is strict, to PH and the strict control of dosage, waste water is qualified discharge stably after treatment.
Claims (9)
1, a kind of treatment process of complete wiring board factory effluent, characteristics according to the wiring board production technique, it is that waste water, nickel are that waste water, silver are that waste water, copper are waste water, stripping ink developer waste water, high-COD waste water and generally wash totally seven kinds in water that the character of its waste water can be divided into gold-plated line cyanogen, it is characterized in that: above-mentioned seven kinds of waste water are collected separately and done handle especially, its concrete treatment process is as follows:
(1), to collect nickel be waste water, in reaction tank, add and remove the nickel agent, by (the Ni≤1mg/l) of qualified discharge behind the coagulating sedimentation;
(2), to collect silver be waste water, by (the Ag≤0.5mg/l) of qualified discharge behind the coagulating sedimentation;
(3), to collect cyanogen be waste water, removes through NaClO under the alkaline condition respectively that NaClO removes cyanogen under cyanogen and the acidic conditions, again by behind the catalytic oxidation degree of depth broken cyanide with general washing water combination treatment;
(4), collect stripping ink developer waste water, after an acidifying, enter the catalytic oxidation pond and handle the back coagulating sedimentation, enter pump well after regulating pH value;
(5), collect high-COD waste water, handle through the catalytic oxidation pond, regulate pH value and mix by the pump well that enters behind the coagulating sedimentation in (4) step;
(6), the waste water in the pump well in (5) step is sterilized after secondary sedimentation, then with general washing water combination treatment through the routine biochemistry pond;
(7), to collect copper be waste water, through overregulating pH value and reduction-replacement process, transferring pH value by hydro-oxidation sodium and calcium hydroxide again is about 9, behind the last coagulating sedimentation with general washing water combination treatment;
(8), the water after the processing of (3) (6) (7) is mixed with general washing water, get final product qualified discharge through conventional wastewater treatment process again, promptly enter clean water basin by reduction-displacement, accent PH coagulating sedimentation, sand filtration, PH terminal after regulating, a part is back to production, other qualified discharge.
2, the treatment process of complete wiring board factory effluent according to claim 1, it is characterized in that: the pH value of described (3) step neutral and alkali condition is about 10.
3, the treatment process of complete wiring board factory effluent according to claim 1, it is characterized in that: the pH value of acidic conditions is about 4 in described (3) step.
4, the treatment process of complete wiring board factory effluent according to claim 1 is characterized in that: acidifying for the first time is to adopt H in described (4) step
2SO
4Acidifying equals about 4 pH value.
5, the treatment process of complete wiring board factory effluent according to claim 1 is characterized in that: regulate about pH value to 7 behind the coagulating sedimentation in described (4) step.
6, the treatment process of complete wiring board factory effluent according to claim 1, it is characterized in that: handle the back through the catalytic oxidation pond in described (5) step and regulate about pH value to 8.5, adopt PAC (aluminium chlorohydroxide), PAM (polyacrylamide) coagulating sedimentation.
7, the treatment process of complete wiring board factory effluent according to claim 1, it is characterized in that: the catalytic oxidation of indication in described (3), (4), (5) step, be under the 3-24V volts DS, between the battery lead plate of special material, filling is furnished with the filler of catalyzer, waste water PH is transferred to about 4,, finish the process of catalytic oxidation through two hours hydraulic detention times.
8, the treatment process of complete wiring board factory effluent according to claim 1 is characterized in that: regulate pH value and reduction-replacement process in described (7) step for using H
2SO
4Regulate the complex compound that makes copper about pH value to 4 and destroy, add FeSO again
47H
2O makes Cu
2+Fe is used in reduction simultaneously
2+Displacement Cu
2+
9, the treatment process of complete wiring board factory effluent according to claim 1 is characterized in that: precipitation process of coagulation adds NaOH and makes about pH value to 9 for adopting in described (7) step, adds Ca (OH) again
2, PAC, PAM, Na
2The S coagulating sedimentation.
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|---|---|---|---|
| CNB2007100746515A CN100519448C (en) | 2007-05-29 | 2007-05-29 | Integrated processing technique for waste water in breadboard production |
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|---|---|---|---|
| CNB2007100746515A CN100519448C (en) | 2007-05-29 | 2007-05-29 | Integrated processing technique for waste water in breadboard production |
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2007
- 2007-05-29 CN CNB2007100746515A patent/CN100519448C/en not_active Expired - Fee Related
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