CN108706803A - A kind of electronic circuit board industry wastewater treatment recovery method - Google Patents
A kind of electronic circuit board industry wastewater treatment recovery method Download PDFInfo
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- CN108706803A CN108706803A CN201810430443.2A CN201810430443A CN108706803A CN 108706803 A CN108706803 A CN 108706803A CN 201810430443 A CN201810430443 A CN 201810430443A CN 108706803 A CN108706803 A CN 108706803A
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- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 13
- 238000011084 recovery Methods 0.000 title claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 67
- 239000007788 liquid Substances 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 26
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 17
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002425 crystallisation Methods 0.000 claims abstract description 16
- 230000008025 crystallization Effects 0.000 claims abstract description 16
- 238000005530 etching Methods 0.000 claims abstract description 15
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 14
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 12
- 238000006481 deamination reaction Methods 0.000 claims abstract description 11
- 238000001556 precipitation Methods 0.000 claims abstract description 11
- 239000012452 mother liquor Substances 0.000 claims abstract description 9
- 230000002378 acidificating effect Effects 0.000 claims abstract description 7
- 239000011780 sodium chloride Substances 0.000 claims abstract description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 7
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 7
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000005751 Copper oxide Substances 0.000 claims abstract description 4
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000000909 electrodialysis Methods 0.000 claims description 18
- 239000012528 membrane Substances 0.000 claims description 18
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 16
- 239000011734 sodium Substances 0.000 claims description 16
- 229910052708 sodium Inorganic materials 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 15
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 10
- 229910001415 sodium ion Inorganic materials 0.000 claims description 10
- 239000002351 wastewater Substances 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 8
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims description 7
- 239000005752 Copper oxychloride Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- HKMOPYJWSFRURD-UHFFFAOYSA-N chloro hypochlorite;copper Chemical compound [Cu].ClOCl HKMOPYJWSFRURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 238000002242 deionisation method Methods 0.000 claims description 6
- 238000005374 membrane filtration Methods 0.000 claims description 6
- 238000006386 neutralization reaction Methods 0.000 claims description 6
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 6
- 238000001223 reverse osmosis Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000004073 vulcanization Methods 0.000 claims description 6
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 238000005352 clarification Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 230000009615 deamination Effects 0.000 claims description 3
- 238000003795 desorption Methods 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 239000013505 freshwater Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 3
- 239000011150 reinforced concrete Substances 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 239000001119 stannous chloride Substances 0.000 claims description 3
- 235000011150 stannous chloride Nutrition 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- -1 iron ion Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 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
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- 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
- C02F1/586—Treatment of water, waste water, or sewage by removing specified dissolved compounds by removing ammoniacal nitrogen
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F2001/5218—Crystallization
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/04—Flow arrangements
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/06—Pressure conditions
- C02F2301/063—Underpressure, vacuum
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a kind of electronic circuit board industry wastewater treatment recovery methods, include the following steps：Water Tank A and Water Tank B is set, acidic etching liquid A and alkaline etching liquid B are passed through into slanting horizontal flow basin respectively, alkaline clear liquid B is placed in deamination reaction device, the aqueous solution containing sodium chloride and sodium sulphate after being chemically reacted in the deamination reaction device of third step is connected to gas-liquid separator by pipeline, isolate ammonia, copper oxide will be added in acid clear liquid, sulfur dioxide gas is passed through in clear solution, when solution becomes light brown from green, stop leading to sulfur dioxide gas, obtain mother liquor, solution cools down, the crystallization of precipitation is filtered out from mother liquor, wastewater treatment recovery method of the present invention, single sodium salt can be recycled, and copper ion can be recycled, produce effects height.
Description
Technical field
The present invention relates to technical field of environment protection equipment, more particularly to a kind of electronic circuit board industry waste water treatment and reclamation side
Method.
Background technology
In existing circuit board etching solution, containing a large amount of ammonium ion, chlorion, iron ion, copper ion, sodium ion,
Sulfate ion, salt acid ion, generally recycles copper ion, and copper ion way of recycling is generally using addition akaline liquid life
At hydroxide copper sludge, residue of mother copper ion vulcanized sodium, which reacts, produces copper sulfide precipitation, in remaining mother liquor and lime and anti-
Hydroxide iron cement, water qualified discharge should be generated, above resource reclaim generally can only obtain single sodium salt, and wastewater treatment
Not exclusively, due to having carried out agent-feeding treatment, the toxicant of water body only temporarily stashes.
Invention content
The invention mainly solves the technical problem of providing a kind of electronic circuit board industry wastewater treatment recovery methods, can
So that various recyclable ions fully recycle, and the waste water generated is few, simple for process, and stability is high.
A kind of electronic circuit board industry wastewater treatment recovery method, includes the following steps：
The first step：Electronic circuit board industry waste water is respectively put into according to acid-base value in Water Tank A and Water Tank B, in Water Tank A
Middle addition reducing agent, and being stirred is generated with containing the acidic etching liquid A based on copper ion and hydrochloric acid, in Water Tank B plus
Enter reducing agent, and be stirred, generates the alkaline etching liquid B containing copper ion and ammonium hydroxide；
Second step：Acidic etching liquid A and alkaline etching liquid B is removed into insoluble substance, then by slanting horizontal flow basin respectively
Acid clear liquid A and alkaline clear liquid B are obtained, the horizontal flow basin uses reinforced concrete structure；
Third walks：Alkaline clear liquid B is placed in deamination reaction device, alkaline matter NaOH is added by alkali charger, deamination
NH4 in reactor in waste water is converted to NH3, and specific method and chemical equation are：First reaction equation be：
NaOH+NH4CL=NaCL+NH3 ↑+H2O, second reaction equation are：(NH4) 2SO4+2NaOH=NA2SO4+2NH3 ↑+2H2O；
4th step：The aqueous solution containing sodium chloride and sodium sulphate after being chemically reacted in the deamination reaction device of third step is passed through into pipe
Road is connected to gas-liquid separator, isolates ammonia；
5th step：Copper oxide will be added in acid clear liquid, adjusts the pH value of solution to 1-1.5；Filtering solution removes insoluble object
Matter obtains clear solution；
6th step：Clear solution in 5th step is heated to 70 DEG C -80 DEG C, stirring clarification is molten under conditions of keeping temperature
Liquid, and it is passed through sulfur dioxide gas into the clear solution, when solution becomes light brown from green, stop leading to sulfur dioxide gas
Body obtains mother liquor；
7th step：By the solution cooling in the 6th step, the crystallization of precipitation is filtered out from above-mentioned mother liquor；
8th step：Solution dilute hydrochloric acid, ethyl alcohol in 7th step are washed into the crystallization filtered out successively, after the dry crystallization,
Obtain stannous chloride；
9th step：Acid solution in alkaline clear liquid body and the 8th step in 4th step is added in reactor and neutralize instead
It answers, neutralization reaction temperature is 75~85 DEG C, and the flow of acid, alkaline two kinds of clear solutions is added in control so that when neutralization reaction
The pH value of reaction solution is 4.5~5.5, is stirred to react liquid until copper oxychloride crystal is precipitated from reaction solution；
Tenth step：Reaction solution filtering in 9th step, obtains copper oxychloride crystal and solution A, is injected into the solution A dense
Degree carries out vulcanization reaction for 35~39% ammonium sulfide solution, copper sulfide precipitation object and B solution is made, wherein the vulcanization being added
The amount of ammonium salt solution is to be enough to form copper sulfide precipitation object；
11st step：Described ground B solution to be sent into reaction kettle and carries out pH value adjusting so that the pH values of B solution are 5~5.5,
Reaction kettle is warming up to 80~90 DEG C of progress negative pressure concentrations again, stops heating after the temperature of B solution is 40~41, obtains residual
Remaining sodium sulphate and a small amount of sodium chloride solution enter low temperature crystallization device by pipeline；
12nd step：The mixed liquor of low temperature crystallization device containing a small amount of sodium ion enters electrodialysis plant by pipeline, by electric osmose
The electrodialytic membranes of desorption device, carries out electrodialysis, a kind of optimal technical scheme, and the electrodialysis plant is electrolytic cell；
13rd step：Into after electrodialytic membranes, the concentration of concentrated water containing sodium ion is increased to 15%, after reaching high concentration sodium salt；
14th step：The fresh water generated by electrodialysis plant, enters sodium membrane filtration；
15th step：Sodium membrane filtration, the filtering light liquid of liquid enter reverse osmosis membrane, and concentrated water containing sodium ion backs within electricity
Electrodialysis equipment carries out electrodialysis, by carrying out circulating filtration after electrodialytic membranes；
16th step：By reverse osmosis membrane, by sodium at high concentration ion concentrated water and deionization pure water, deionization pure water is obtained by filtration
Discharge, sodium at high concentration ion concentrated water enter sodium filter membrane and filter again, and process is utilized to complete entire waste water resource.
The beneficial effects of the invention are as follows：A kind of electronic circuit board industry wastewater treatment recovery method of the present invention, can recycle
Single sodium salt, and copper ion can be recycled, production method is simple, and produce effects height.
Specific implementation mode
The preferred embodiments of the present invention will be described in detail below so that advantages and features of the invention can be easier to by
It will be appreciated by those skilled in the art that so as to make a clearer definition of the protection scope of the present invention.
A kind of electronic circuit board industry wastewater treatment recovery method, includes the following steps：
The first step：Electronic circuit board industry waste water is respectively put into according to acid-base value in Water Tank A and Water Tank B, in Water Tank A
Middle addition reducing agent, and being stirred is generated with containing the acidic etching liquid A based on copper ion and hydrochloric acid, in Water Tank B plus
Enter reducing agent, and be stirred, generates the alkaline etching liquid B containing copper ion and ammonium hydroxide；
Second step：Acidic etching liquid A and alkaline etching liquid B is removed into insoluble substance, then by slanting horizontal flow basin respectively
Acid clear liquid A and alkaline clear liquid B are obtained, the horizontal flow basin uses reinforced concrete structure；
Third walks：Alkaline clear liquid B is placed in deamination reaction device, alkaline matter NaOH is added by alkali charger, deamination
NH4 in reactor in waste water is converted to NH3, and specific method and chemical equation are：First reaction equation be：
NaOH+NH4CL=NaCL+NH3 ↑+H2O, second reaction equation are：(NH4) 2SO4+2NaOH=NA2SO4+2NH3 ↑+2H2O；
4th step：The aqueous solution containing sodium chloride and sodium sulphate after being chemically reacted in the deamination reaction device of third step is passed through into pipe
Road is connected to gas-liquid separator, isolates ammonia；
5th step：Copper oxide will be added in acid clear liquid, adjusts the pH value of solution to 1-1.5；Filtering solution removes insoluble object
Matter obtains clear solution；
6th step：Clear solution in 5th step is heated to 70 DEG C -80 DEG C, stirring clarification is molten under conditions of keeping temperature
Liquid, and it is passed through sulfur dioxide gas into the clear solution, when solution becomes light brown from green, stop leading to sulfur dioxide gas
Body obtains mother liquor；
7th step：By the solution cooling in the 6th step, the crystallization of precipitation is filtered out from above-mentioned mother liquor；
8th step：Solution dilute hydrochloric acid, ethyl alcohol in 7th step are washed into the crystallization filtered out successively, after the dry crystallization,
Obtain stannous chloride；
9th step：Acid solution in alkaline clear liquid body and the 8th step in 4th step is added in reactor and neutralize instead
It answers, neutralization reaction temperature is 75~85 DEG C, and the flow of acid, alkaline two kinds of clear solutions is added in control so that when neutralization reaction
The pH value of reaction solution is 4.5~5.5, is stirred to react liquid until copper oxychloride crystal is precipitated from reaction solution；
Tenth step：Reaction solution filtering in 9th step, obtains copper oxychloride crystal and solution A, is injected into the solution A dense
Degree carries out vulcanization reaction for 35~39% ammonium sulfide solution, copper sulfide precipitation object and B solution is made, wherein the vulcanization being added
The amount of ammonium salt solution is to be enough to form copper sulfide precipitation object；
11st step：Described ground B solution to be sent into reaction kettle and carries out pH value adjusting so that the pH values of B solution are 5~5.5,
Reaction kettle is warming up to 80~90 DEG C of progress negative pressure concentrations again, stops heating after the temperature of B solution is 40~41, obtains residual
Remaining sodium sulphate and a small amount of sodium chloride solution enter low temperature crystallization device by pipeline；
12nd step：The mixed liquor of low temperature crystallization device containing a small amount of sodium ion enters electrodialysis plant by pipeline, by electric osmose
The electrodialytic membranes of desorption device, carries out electrodialysis, a kind of optimal technical scheme, and the electrodialysis plant is electrolytic cell；
13rd step：Into after electrodialytic membranes, the concentration of concentrated water containing sodium ion is increased to 15%, after reaching high concentration sodium salt；
14th step：The fresh water generated by electrodialysis plant, enters sodium membrane filtration；
15th step：Sodium membrane filtration, the filtering light liquid of liquid enter reverse osmosis membrane, and concentrated water containing sodium ion backs within electricity
Electrodialysis equipment carries out electrodialysis, by carrying out circulating filtration after electrodialytic membranes；
16th step：By reverse osmosis membrane, by sodium at high concentration ion concentrated water and deionization pure water, deionization pure water is obtained by filtration
Discharge, sodium at high concentration ion concentrated water enter sodium filter membrane and filter again, and process is utilized to complete entire waste water resource.
Example the above is only the implementation of the present invention is not intended to limit the scope of the invention, every to utilize this hair
Equivalent structure or equivalent flow shift made by bright description is applied directly or indirectly in other relevant technology necks
Domain is included within the scope of the present invention.
Claims (3)
1. a kind of electronic circuit board industry wastewater treatment recovery method, which is characterized in that include the following steps：
The first step：Electronic circuit board industry waste water is respectively put into according to acid-base value in Water Tank A and Water Tank B, in Water Tank A
Middle addition reducing agent, and being stirred is generated with containing the acidic etching liquid A based on copper ion and hydrochloric acid, in Water Tank B plus
Enter reducing agent, and be stirred, generates the alkaline etching liquid B containing copper ion and ammonium hydroxide；
Second step：Acidic etching liquid A and alkaline etching liquid B is removed into insoluble substance, then by slanting horizontal flow basin respectively
Acid clear liquid A and alkaline clear liquid B are obtained,
Third walks：Alkaline clear liquid B is placed in deamination reaction device, alkaline matter NaOH is added by alkali charger, deamination
NH4 in reactor in waste water is converted to NH3, and specific method and chemical equation are：First reaction equation be：
NaOH+NH4CL=NaCL+NH3 ↑+H2O, second reaction equation are：(NH4) 2SO4+2NaOH=NA2SO4+2NH3 ↑+2H2O；
4th step：The aqueous solution containing sodium chloride and sodium sulphate after being chemically reacted in the deamination reaction device of third step is passed through into pipe
Road is connected to gas-liquid separator, isolates ammonia；
5th step：Copper oxide will be added in acid clear liquid, adjusts the pH value of solution to 1-1.5；Filtering solution removes insoluble object
Matter obtains clear solution；
6th step：Clear solution in 5th step is heated to 70 DEG C -80 DEG C, stirring clarification is molten under conditions of keeping temperature
Liquid, and it is passed through sulfur dioxide gas into the clear solution, when solution becomes light brown from green, stop leading to sulfur dioxide gas
Body obtains mother liquor；
7th step：By the solution cooling in the 6th step, the crystallization of precipitation is filtered out from above-mentioned mother liquor；
8th step：Solution dilute hydrochloric acid, ethyl alcohol in 7th step are washed into the crystallization filtered out successively, after the dry crystallization,
Obtain stannous chloride；
9th step：Acid solution in alkaline clear liquid body and the 8th step in 4th step is added in reactor and neutralize instead
It answers, neutralization reaction temperature is 75~85 DEG C, and the flow of acid, alkaline two kinds of clear solutions is added in control so that when neutralization reaction
The pH value of reaction solution is 4.5~5.5, is stirred to react liquid until copper oxychloride crystal is precipitated from reaction solution；
Tenth step：Reaction solution filtering in 9th step, obtains copper oxychloride crystal and solution A, is injected into the solution A dense
Degree carries out vulcanization reaction for 35~39% ammonium sulfide solution, copper sulfide precipitation object and B solution is made, wherein the vulcanization being added
The amount of ammonium salt solution is to be enough to form copper sulfide precipitation object；
11st step：Described ground B solution to be sent into reaction kettle and carries out pH value adjusting so that the pH values of B solution are 5~5.5,
Reaction kettle is warming up to 80~90 DEG C of progress negative pressure concentrations again, stops heating after the temperature of B solution is 40~41, obtains residual
Remaining sodium sulphate and a small amount of sodium chloride solution enter low temperature crystallization device by pipeline；
12nd step：The mixed liquor of low temperature crystallization device containing a small amount of sodium ion enters electrodialysis plant by pipeline, by electric osmose
The electrodialytic membranes of desorption device carries out electrodialysis；
13rd step：Into after electrodialytic membranes, the concentration of concentrated water containing sodium ion is increased to 15%, after reaching high concentration sodium salt；
14th step：The fresh water generated by electrodialysis plant, enters sodium membrane filtration；
15th step：Sodium membrane filtration, the filtering light liquid of liquid enter reverse osmosis membrane, and concentrated water containing sodium ion backs within electricity
Electrodialysis equipment carries out electrodialysis, by carrying out circulating filtration after electrodialytic membranes；
16th step：By reverse osmosis membrane, by sodium at high concentration ion concentrated water and deionization pure water, deionization pure water is obtained by filtration
Discharge, sodium at high concentration ion concentrated water enter sodium filter membrane and filter again, and process is utilized to complete entire waste water resource.
2. a kind of electronic circuit board industry wastewater treatment recovery method according to claim 1, in the second step, put down
It flows pond and uses reinforced concrete structure.
3. a kind of electronic circuit board industry wastewater treatment recovery method according to claim 1, in the 12nd step,
Electrodialysis plant is electrolytic cell.
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| CN113501592A (en) * | 2021-06-25 | 2021-10-15 | 深圳市宏联电路有限公司 | Microwave circulation treatment system and process for waste etching liquid of printed circuit board |
| CN114772628A (en) * | 2022-04-22 | 2022-07-22 | 盛隆资源再生（无锡）有限公司 | Method for recovering waste etching liquid |
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