CN103787400A - Method for treating microetching liquid waste and copper sulfate liquid waste - Google Patents
Method for treating microetching liquid waste and copper sulfate liquid waste Download PDFInfo
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- CN103787400A CN103787400A CN201310742385.4A CN201310742385A CN103787400A CN 103787400 A CN103787400 A CN 103787400A CN 201310742385 A CN201310742385 A CN 201310742385A CN 103787400 A CN103787400 A CN 103787400A
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- cupric oxide
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- microetch
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- 238000000034 method Methods 0.000 title claims abstract description 81
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 title claims abstract description 46
- 229910000365 copper sulfate Inorganic materials 0.000 title claims abstract description 40
- 239000010808 liquid waste Substances 0.000 title abstract 11
- 239000002699 waste material Substances 0.000 claims abstract description 175
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 155
- 239000007788 liquid Substances 0.000 claims abstract description 125
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052802 copper Inorganic materials 0.000 claims abstract description 47
- 239000010949 copper Substances 0.000 claims abstract description 47
- 239000002253 acid Substances 0.000 claims abstract description 33
- 239000011259 mixed solution Substances 0.000 claims abstract description 17
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229960004643 cupric oxide Drugs 0.000 claims description 80
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 72
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 55
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 49
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 37
- 239000003513 alkali Substances 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000013078 crystal Substances 0.000 claims description 24
- 239000012452 mother liquor Substances 0.000 claims description 23
- 229910052742 iron Inorganic materials 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 21
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- XEMZLVDIUVCKGL-UHFFFAOYSA-N hydrogen peroxide;sulfuric acid Chemical compound OO.OS(O)(=O)=O XEMZLVDIUVCKGL-UHFFFAOYSA-N 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 18
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 14
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 13
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 238000002425 crystallisation Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 11
- 229920002401 polyacrylamide Polymers 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- 235000017550 sodium carbonate Nutrition 0.000 claims description 10
- PANBYUAFMMOFOV-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [Na].OS(O)(=O)=O PANBYUAFMMOFOV-UHFFFAOYSA-N 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 8
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 239000000701 coagulant Substances 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 3
- 235000015320 potassium carbonate Nutrition 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 10
- 239000005751 Copper oxide Substances 0.000 abstract description 7
- 229910000431 copper oxide Inorganic materials 0.000 abstract description 7
- 238000009713 electroplating Methods 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 4
- 229910001431 copper ion Inorganic materials 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000003247 decreasing effect Effects 0.000 abstract 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 16
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 14
- 238000000967 suction filtration Methods 0.000 description 13
- 239000007790 solid phase Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 230000002829 reductive effect Effects 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 8
- 239000002351 wastewater Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 229910001448 ferrous ion Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 5
- 239000012028 Fenton's reagent Substances 0.000 description 5
- 238000011109 contamination Methods 0.000 description 5
- 239000003456 ion exchange resin Substances 0.000 description 5
- 229920003303 ion-exchange polymer Polymers 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 229910052785 arsenic Inorganic materials 0.000 description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000003984 copper intrauterine device Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 230000005068 transpiration Effects 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- -1 iron ion Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 150000002978 peroxides Chemical group 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Abstract
The invention discloses a method for treating microetching liquid waste and copper sulfate liquid waste. The method is characterized in that usable materials in the microetching liquid waste and copper sulfate liquid waste are utilized, and the reasonable process conditions are controlled, so as to reach the purpose of treatment of wastes with processes of wastes against one another; in addition, the COD (Chemical Oxygen Demand) value in the mixed solution of the microetching liquid waste and copper sulfate liquid waste is greatly decreased, the copper-iron separation is effectively carried out, and as a result, copper ions in the microetching liquid waste and copper sulfate liquid waste can be further recycled. According to the method, the COD in the prepared mixed copper-containing liquid waste is decreased by more than 98.5%; under the control on the process conditions, the copper-containing acid liquid obtained by the method can be used for producing electroplating grade copper oxide or electroplating grade copper sulfate, and thus the waste is turned into wealth.
Description
Technical field
The invention belongs to waste liquid and recycle field, relate to a kind of microetch waste liquid and bluestone waste treatment process, be specifically related to a kind of novel method of utilizing microetch waste liquid and bluestone waste to prepare plating-grade copper oxide or cupric sulfate purified.
Background technology
In the PCB circuit card course of processing, apply in the pretreatment procedure of processing at plating hole, internal layer/laminated and photoresist layer, solder mask, effectively microetch not only can make the result of use of plate good, and work-ing life that can extension plate.Traditional PCB microetch system is peroxide systems, be mainly sulfuric acid-hydrogen peroxide system and sulfuric acid-Sodium Persulfate system, micro etching solution can clean plate in a certain amount of copper of microetch the dirt such as face fingerprint, oxide compound and organic contamination, after processing, form microetch waste liquid.This waste liquid copper content is low, and COD content is high, and recycling difficulty is larger, and directly discharge meeting causes severe contamination to environment.
In the PCB circuit board electroplating course of processing, the copper-plating technique using is the replacement(metathesis)reaction of iron and cupric ion, in the time that copper ion concentration drops to certain value, copper facing reaction can not normally be carried out, and must add the organic additives such as appropriate copper-bath, brightening agent, leveling agent; And in the time that the ferrous ion concentration producing after reaction rises to certain value, copper facing reaction can not normally be carried out, become cupric waste plating solution, must be discharged production line, supplement new plating solution.And electroplate a large amount of clear water rinsings for circuit card after processing, the waste water after rinsing and cupric waste plating solution mix, and have produced bluestone waste.This waste liquid copper content is low, and COD content is high, and recycling difficulty is larger, and directly discharge meeting causes severe contamination to environment.
The treatment process of existing microetch waste liquid is as follows:
1. metal replacement method: metal replacement method is the difference based on metal activity, joins more active iron powder or aluminium powder in microetch waste liquid, and cupric ion is reduced into copper sponge.The method is low to the rate of recovery of copper, and the copper sponge purity obtaining after displacement is lower, still has a large amount of sulfuric acid, COD and a certain amount of copper in waste liquid, and directly discharge will cause secondary pollution to environment;
2. neutralization precipitation method: neutralization precipitation method is with alkali (caustic soda, sodium carbonate etc.), the sulfuric acid in microetch waste liquid is neutralized and copper is precipitated as to cupric oxide or ventilation breather etc., but owing to containing a large amount of COD in microetch waste liquid, directly add alkali and be precipitated as mantoquita, easily cause the also co-precipitation together of COD in microetch waste liquid, cause that the crystal formation of mantoquita is bad and copper content is on the low side.And still contain the COD of higher concentration in microetch waste liquid after heavy copper, if do not process direct discharge, can cause severe contamination to environment; And if to process, select biochemical rule to affect microorganism active because of the strong oxidizer such as hydrogen peroxide or Sodium Persulfate in waste water, cause difficult treatment; Easily cause film to stop up if select ultrafiltrationmembrane process to process, and consumables cost is higher, the larger molecular organics dope after holding back also needs to carry out subsequent disposal; If energy consumption is too high for the method for selection evaporation concentration;
3. electrodip process: utilize acid copper technique to process microetch waste liquid, though can obtain the tabular copper of electrolysis, but it is high to process energy consumption, and micro-etched waste liquid makes the oxygenant such as Sodium Persulfate and hydrogen peroxide be reduced under the reductive action of electrode cathode, not only cause the wasting of resources of these oxygenants, and COD in waste water still do not remove, still need further processing.
The treatment process of existing bluestone waste is as follows:
1. metal replacement method: metal replacement method is the difference based on metal activity, joins more active iron powder or aluminium powder in bluestone waste, and cupric ion is reduced into copper sponge.The method is low to the rate of recovery of copper, and the copper sponge purity obtaining after displacement is lower, still has a large amount of sulfuric acid, COD and a certain amount of copper in waste liquid, and directly discharge will cause secondary pollution to environment.
2. neutralization precipitation method: neutralization precipitation method is with alkali (caustic soda, sodium carbonate etc.), the sulfuric acid in bluestone waste is neutralized and copper is precipitated as to cupric oxide or ventilation breather etc., but owing to containing a large amount of COD in bluestone waste, directly add alkali and be precipitated as mantoquita, easily cause the also co-precipitation together of COD in bluestone waste, cause that the crystal formation of mantoquita is bad and copper content is on the low side.And still contain the COD of higher concentration in bluestone waste after heavy copper, if do not process direct discharge, can cause severe contamination to environment; And if to process, select biochemical rule because the ferrous ion in waste water and iron concentration are compared with the high microorganism active that affects, to cause difficult treatment; Easily cause film to stop up if select ultrafiltrationmembrane process to process, and consumables cost is higher, the larger molecular organics dope after holding back also needs to carry out subsequent disposal; If energy consumption is too high for the method for selection evaporation concentration.
3. electrodip process: utilize acid copper technique to process bluestone waste, though can obtain the tabular copper of electrolysis, process energy consumption high, and after recovery copper, the COD in waste liquid does not still remove, and still needs further processing.
In sum, all there is the problems such as energy consumption is large, and efficiency is low in the method for the existing processing to microetch waste liquid and bluestone waste.
Summary of the invention
The object of the invention is to overcome the defect of prior art, the treatment process of a kind of microetch waste liquid and bluestone waste is provided, the method can make full use of the effective constituent in microetch waste liquid and bluestone waste, almost entirely remove the COD in waste liquid, the separation of the metal ion in waste liquid is had to unusual effect simultaneously, the remaining liquid that utilizes this treatment process to obtain, can be for the production of cupric oxide or copper sulfate product, the cupric oxide copper sulfate product purity obtaining is high, even can produce plating-grade copper oxide or cupric sulfate purified by the control of technique.
Above-mentioned purpose of the present invention is achieved by following technical solution:
A treatment process for microetch waste liquid and bluestone waste, comprises the following steps:
S1. preparation mixes contained waste liquid: the microetch waste liquid of sulfuric acid-hydrogen peroxide system is mixed with bluestone waste, obtain mixing contained waste liquid, make to mix copper content 7 ~ 10g/L in contained waste liquid, iron level 0.3 ~ 1g/L, COD content 2000 ~ 4000mg/L, hydrogen peroxide content 0.5 ~ 5mL/L;
S2. removing COD and copper iron separates: regulate the pH value of mixing contained waste liquid 2.5 ~ 3.2, add the ironic hydroxide of 20 ~ 50g and the hydrogen peroxide that is 18 ~ 24g by significant quantity calculated mass by every L mixing contained waste liquid, and stirring reaction 1 ~ 3 hour, then add coagulant aids; After completion of the reaction, filter, collect solid formation, rinsing solid formation 2 ~ 3 times, and collect filtrate and float scrub raffinate.
In the microetch waste liquid of sulfuric acid-hydrogen peroxide system that common process is produced, contain copper 7 ~ 10g/L, hydrogen peroxide 2 ~ 20mL/L, COD6000 ~ 9000mg/L; In the bluestone waste that common process is produced, contain copper 7 ~ 10g/L, ferrous 2 ~ 3g/L, COD1000 ~ 3000mg/L.
Prior art is only to process for above-mentioned waste liquid separately, fails to make full use of the useful matter in waste liquid.
Contriver finds, these waste liquids are mixed to form to mixed solution according to certain ratio, can make full use of the useful matter in these waste liquids, realizes the object of the treatment of wastes with processes of wastes against one another.Specifically utilize hydrogen peroxide in the microetch waste liquid of sulfuric acid-hydrogen peroxide system and the ferrous ion in bluestone waste can form Fenton reagent (Fenton Agent), under rational ratio, regulate again the pH value of mixed solution, coordinate appropriate hydrogen peroxide, the efficiency that makes on the one hand Fenton reagent oxidation mix the COD in microetch waste liquid and bluestone waste reaches higher level, can save on the other hand the interpolation of ferrous iron and hydrogen peroxide, really accomplish the treatment of wastes with processes of wastes against one another, economize in raw materials.
Utilize the microetch waste liquid of sulfuric acid-hydrogen peroxide system contained and the hydrogen peroxide that added afterwards, with the ferrous ion composition Fenton reagent in bluestone waste, be oxidized after the COD in mixing contained waste liquid, the ferrous iron in bluestone waste is oxidized to ferric iron completely by excessive hydrogen peroxide; Utilize the ironic hydroxide adding as coagulating agent and crystal seed, the complete coagulation of ironic hydroxide that impels reaction to form, and can recycle, and precipitated copper not substantially, in effectively removing COD, realized effective separation of copper, iron.
As a kind of possibility, S1. in, beyond the microetch waste liquid of sulfuric acid-hydrogen peroxide system, the microetch waste liquid that can also add a small amount of sulfuric acid-Sodium Persulfate system mixes with bluestone waste, in the microetch waste liquid of sulfuric acid-Sodium Persulfate system that common process is produced, contain copper 7 ~ 10g/L, persulfate 5 ~ 10g/L, COD6000 ~ 9000mg/L; Utilize persulfate part ferrous ion in system can be oxidized to iron ion, thereby reduce the add-on of hydrogen peroxide.But may have disadvantageous effect excessive the adding of persulfate to Fenton reagent, therefore can control the amount of the persulfate of adding.
As a kind of preferred version, S1. in, the microetch waste liquid of the microetch waste liquid of sulfuric acid-hydrogen peroxide system, sulfuric acid-Sodium Persulfate system is mixed with bluestone waste, obtain mixing contained waste liquid, make to mix copper content 7 ~ 10g/L in contained waste liquid, iron level 0.3 ~ 1g/L, COD content 2000 ~ 4000mg/L, hydrogen peroxide content 0.5 ~ 5mL/L, persulfate content 0.2 ~ 1g/L.
The actual interpolation volume of hydrogen peroxide is relevant with the concentration of the hydrogen peroxide of selecting, as long as in the hydrogen peroxide adding, the content of active substance reaches above-mentioned scope, can realize the application's goal of the invention.
Contriver confirms by experiment, the filtrate obtaining through above-mentioned disposal methods with float scrub raffinate compared with before processing, the clearance of the COD in system is greater than 98.5%.
In the waste liquid that the blending ratio of microetch waste liquid and bluestone waste can adopt according to reality, corresponding substances content determines, makes the substances content of gained mixing contained waste liquid fall into above-mentioned scope.
Adopt microetch waste liquid and bluestone waste to prepare a method for cupric oxide, comprise the steps:
Obtain according to the method described above filtrate and float the mixed solution of scrub raffinate, take described filtrate and the mixed solution that floats scrub raffinate as raw material, prepare cupric oxide.Preparing the method for cupric oxide can carry out with reference to prior art, as disclosed technology in CN201110396253.1.
As more preferably scheme of one, under prepare cupric oxide step and preferably carry out as follows, comprise the steps:
S31. join alkali: prepare mixed alkali liquor, described mixed alkali liquor is that highly basic and strong base-weak acid salt dissolve the aqueous solution obtaining; The mass ratio of described mixed alkali liquor strong base-weak acid salt and highly basic is 1:3 ~ 1:5,, described mixed alkali liquor mass concentration is 15%, described highly basic is any one or its mixture in sodium hydroxide or potassium hydroxide; Described strong base-weak acid salt is any one or a few in sodium carbonate, salt of wormwood, sodium bicarbonate or saleratus;
S32. prepare cupric oxide wet brilliant: with clear water or cupric oxide mother liquor as reaction mother liquor, control temperature between 80 ~ 85 ℃, add mixed alkali liquor described in cupric acid solution described in step S2 and step S31, control pH value between 8.5 ~ 10.0, react 3 ~ 4 hours, obtain the wet crystal of cupric oxide;
S33. filtration, the wet crystal of rinsing cupric oxide 2 ~ 3 times;
S34. dry roasting, roasting oxidation copper; Described maturing temperature is 400 ℃, and roasting time is 1.5h.
The cupric oxide purity that adopts aforesaid method to prepare is high, and impurity is few, and more than in the product of preparation, the content of cupric oxide can reach 99.1 % by weight, chloride is less than 20ppm, meets the needs of electroplating level.
Adopt microetch waste liquid and bluestone waste to prepare a method for copper sulfate, comprise the steps:
Obtain according to the method described above filtrate and float the mixed solution of scrub raffinate, take described filtrate and the mixed solution that floats scrub raffinate as raw material, take described filtrate and the mixed solution that floats scrub raffinate as raw material, prepare cupric oxide.Preparing the method for cupric oxide can carry out with reference to prior art, as disclosed technology in CN201110396253.1.With clear water or copper sulfate mother liquor, as mother liquor, the cupric oxide of preparation, with cupric oxide described in concentrated sulfuric acid dissolution, regulates pH value to acid, and control temperature of reaction, more than 80 ℃, then, by reaction solution press filtration, crystallisation by cooling, washing, obtains copper sulfate.
As more preferably scheme of one, the preparation method of described copper sulfate, is performed as follows:
S1. preparation mixes contained waste liquid: the microetch waste liquid of sulfuric acid-hydrogen peroxide system is mixed with bluestone waste, obtain mixing contained waste liquid, make to mix copper content 7 ~ 10g/L in contained waste liquid, iron level 0.3 ~ 1g/L, COD content 2000 ~ 4000mg/L, hydrogen peroxide content 0.5 ~ 5mL/L;
S2. removing COD and copper iron separates: regulate the pH value of mixing contained waste liquid 2.5 ~ 3.2, add the ironic hydroxide of 20 ~ 50g and the hydrogen peroxide that 60 ~ 80mL mass concentration is 27.5% by every L mixing contained waste liquid, and stirring reaction 1 ~ 3 hour, then add coagulant aids; After completion of the reaction, filter, collect solid formation, rinsing solid formation 2 ~ 3 times, and collect filtrate and float scrub raffinate, as cupric acid solution;
S3. cupric oxide preparation:
S31. join alkali: prepare mixed alkali liquor, described mixed alkali liquor is that highly basic and strong base-weak acid salt dissolve the aqueous solution obtaining; The mass ratio of described mixed alkali liquor strong base-weak acid salt and highly basic is 1:3 ~ 1:5,, described mixed alkali liquor mass concentration is 15%, described highly basic is any one or its mixture in sodium hydroxide or potassium hydroxide; Described strong base-weak acid salt is any one or a few in sodium carbonate, salt of wormwood, sodium bicarbonate or saleratus;
S32. prepare cupric oxide wet brilliant: with clear water or cupric oxide mother liquor as reaction mother liquor, control temperature between 80 ~ 85 ℃, add mixed alkali liquor described in cupric acid solution described in step S2 and step S31, control pH value between 8.5 ~ 10.0, react 3 ~ 4 hours, obtain the wet crystal of cupric oxide;
S33. filtration, the wet crystal of rinsing cupric oxide 2 ~ 3 times;
S4. prepare copper sulfate: as mother liquor, add the wet crystal of cupric oxide after rinsing, with concentrated sulfuric acid dissolution with clear water or copper sulfate mother liquor, regulating pH value is 1.5 ~ 2.0, control 85 ~ 100 ℃ of temperature and react, press filtration after completion of the reaction, crystallization, washing, obtain copper sulfate.
In the above-mentioned method of preparing copper sulfate, S1. in, beyond the microetch waste liquid of sulfuric acid-hydrogen peroxide system, the microetch waste liquid that can also add a small amount of sulfuric acid-Sodium Persulfate system mixes with bluestone waste, make to mix copper content 7 ~ 10g/L in contained waste liquid, iron level 0.3 ~ 1g/L, COD content 2000 ~ 4000mg/L, hydrogen peroxide content 0.5 ~ 5mL/L, persulfate content 0.2 ~ 1g/L.
The copper sulfate purity that adopts above-mentioned any method to prepare is high, and impurity is few, and more than in the product of preparation, the content of copper sulfate can reach 99.1 % by weight, chloride is less than 12ppm, meets the needs of electroplating level.
As a kind of preferred version, in step S2, regulating pH value can be in system, to add alkali or alkali lye.Described alkali can be selected from sodium hydroxide, potassium hydroxide or its mixture.
Filter type described in the present invention is preferably suction filtration.
As a kind of preferred version, in step S2, described coagulant aids is preferably polyacrylamide.Described polyacrylamide can be the polyacrylamide of cationic, anionic or non-ionic type.
In step S2, the main component of the solid formation after rinsing is ironic hydroxide, and therefore, it can be for the separation of copper iron or brickmaking or iron and steel smelting.
In step S33, the processing mode of the waste water of production cupric oxide routinely technology is carried out.As a kind of preferred version, the processing mode of producing the waste water of cupric oxide in step S33 comprises the steps: filtered liquid and the rinse water of mixed oxidization copper, after precipitation, first spent ion exchange resin is removed wherein remaining cupric ion, make content of copper ion lower than 0.5mg/L, make sal glauberi by concentrating under reduced pressure crystallization again, the saturated rear dilute sulfuric acid dip decopper(ing) of using of described ion exchange resin absorption, makes copper-bath; Described copper-bath can be used as the copper sulfate mother liquor of step S4.
Because concentration technology of the present invention is concentrating under reduced pressure, therefore can save the consumption of steam, reach energy-conservation object.The present invention can fully recycle extracted the salinity in waste water after copper and concentrated after water coolant, and there is no three waste discharge.
Compared with prior art, the present invention has following beneficial effect:
The present invention utilizes the hydrogen peroxide in the microetch waste liquid of sulfuric acid-hydrogen peroxide system and the composition of the ferrous ion in bluestone waste Fenton reagent, by the ratio of rational allocation mixed solution and suitable technique, make effectively being removed of COD in mixed solution, fully realized the treatment of wastes with processes of wastes against one another;
Concentration technology of the present invention is concentrating under reduced pressure, therefore can save the consumption of steam, reaches energy-conservation object, in addition, fully recycle carried the salinity in waste water after copper and concentrated after water coolant, and there is no three waste discharge; Energy consumption is low, non-pollution discharge,
Product purity is high.The COD reduction of preparing the described mixing contained waste liquid of gained through present method is greater than 98.5%.
By the control to processing condition, can also utilize microetch waste liquid and bluestone waste to produce cupric oxide content and be greater than 99.1 % by weight, chloride is less than the plating-grade copper oxide of 20ppm; Copper sulfate content is greater than 99.1 % by weight, and compound content is less than the cupric sulfate purified of 12ppm.
Embodiment
Below in conjunction with specific embodiment, the present invention is explained further, but embodiments of the present invention is not limited in any way.
In embodiment, the microetch waste liquid parameter of sulfuric acid-hydrogen peroxide system used is as follows:
| Copper content, g/L | Iron, mg/L | Arsenic, mg/L | Cadmium, mg/L | Mercury, mg/L | Lead, mg/L | Hydrogen peroxide, mL/L | COD，mg/L |
| 7~10 | 10~50 | <1 | <1 | <1 | <1 | 2~20 | 3000~6000 |
The microetch waste liquid parameter of sulfuric acid-Sodium Persulfate system used is as follows:
| Copper content, g/L | Iron, mg/L | Arsenic, mg/L | Cadmium, mg/L | Mercury, mg/L | Lead, mg/L | Sodium Persulfate, g/L | COD，mg/L |
| 7~10 | 10~50 | <1 | <1 | <1 | <1 | 5~10 | 3000~6000 |
Bluestone waste parameter is as follows:
| Copper content, g/L | Iron, g/L | Arsenic, mg/L | Cadmium, mg/L | Mercury, mg/L | Lead, mg/L | COD，mg/L |
| 7~10 | 2~3 | <1 | <1 | <1 | <1 | 1000~3000 |
Embodiment 1
Microetch waste liquid and bluestone waste utilize a method, comprise the following steps:
S1. preparation mixes contained waste liquid: microetch waste liquid 4000mL and the cupric 9.4g/L of sulfuric acid-hydrogen peroxide system of cupric 9.0g/L, hydrogen peroxide 10mL/L, COD3542mg/L, the bluestone waste 1000mL of ferrous 2.1g/L, COD2211mg/L are mixed, obtain mixing contained waste liquid 5000mL;
S2. removing COD and copper iron separates: 285g powdered sodium carbonate is slowly added and mixed in contained waste liquid, make the pH value of system 2.5, add the ironic hydroxide of 30g and the hydrogen peroxide that 417mL massfraction is 27.5%, stir 1h, adding 0.5mL mass concentration is 0.1% cationic-type polyacrylamide again, and stirring reaction 5 minutes filters, rinsing solid phase 2 times, use 50mL water rinse, gained suction filtration liquid and rinse water to be mixed to get cupric acid solution 5530mL at every turn; The main solid phase residue weight containing ironic hydroxide after rinsing is 38g;
S3. prepare cupric oxide:
S31. join alkali: with 150g sodium hydroxide and 150g sodium carbonate, adding clear water 2700mL, to be made into concentration be 10% mixed alkali liquor;
S32. prepare cupric oxide wet brilliant: as reaction mother liquor, control temperature 60 C with 1000mL clear water, add mixed alkali liquor described in cupric acid solution described in step S2 and step S31, control pH value 8.5, react 5 hours, obtain the wet crystal 80g of cupric oxide;
S33. filtration, the wet crystal of rinsing cupric oxide 2 times are used 100mL water rinse at every turn; After dry, with 300 ℃ of roastings 2 hours, obtain plating-grade copper oxide crystal 58g;
S34. the suction filtration liquid of cupric oxide is mixed with rinse water, obtain mixed solution 7840mL, after precipitation, first spent ion exchange resin is removed wherein remaining cupric ion, make it lower than 0.5mg/L, by concentrating under reduced pressure crystallization, obtain technical grade sal glauberi again, the water after transpiration cooling can be back to production.
In the present embodiment step S2, the cupric acid solution COD making is 20mg/L, copper content 9.1g/L, iron level 7.4mg/L.The clearance of COD is 99.6%.
The cupric oxide product cupric oxide content that the present embodiment prepares is 99.1%, and chloride content is 20ppm.
Embodiment 2
Microetch waste liquid and bluestone waste utilize a method, comprise the following steps:
S1. preparation mixes contained waste liquid: microetch waste liquid 4000mL and the cupric 10.0g/L of sulfuric acid-hydrogen peroxide system of cupric 10.0g/L, hydrogen peroxide 8mL/L, COD4156mg/L, the bluestone waste 800mL of ferrous 3.1g/L, COD1569mg/L are mixed, obtain mixing contained waste liquid 4800mL;
S2. removing COD and copper iron separates: 333mL50% sodium hydroxide solution is slowly added and mixed in contained waste liquid, make the pH value of system 3.0, add the ironic hydroxide of 20g and the hydrogen peroxide that 251mL massfraction is 35%, stir 1h, adding 1.5mL mass concentration is 0.1% anion-polyacrylamide again, and stirring reaction 8 minutes filters, rinsing solid phase 3 times, use 25mL water rinse, gained suction filtration liquid and rinse water to be mixed to get cupric acid solution 5450mL at every turn; The main solid phase residue weight containing ironic hydroxide after rinsing is 23g;
S3. prepare cupric oxide:
S31. join alkali: with 300g sodium hydroxide and 150g sodium carbonate, adding clear water 2550mL, to be made into concentration be 15% mixed alkali liquor;
S32. prepare cupric oxide wet brilliant: as reaction mother liquor, control 90 ℃ of temperature with 1000mL cupric oxide mother liquor, add mixed alkali liquor described in cupric acid solution described in step S2 and step S31, control pH value 9.5, react 3 hours, obtain the wet crystal 82g of cupric oxide;
S33. filtration, the wet crystal of rinsing cupric oxide 2 times are used 100mL water rinse at every turn; After dry, with 400 ℃ of roastings 1.5 hours, obtain plating-grade copper oxide crystal 57g;
S34. the suction filtration liquid of cupric oxide is mixed with rinse water, obtain mixed solution 7000mL, after precipitation, first spent ion exchange resin is removed wherein remaining cupric ion, make it lower than 0.5mg/L, by concentrating under reduced pressure crystallization, obtain technical grade sal glauberi again, the water after transpiration cooling can be back to production.
In the present embodiment step S2, the cupric acid solution COD making is 31mg/L, copper content 10.0g/L, iron level 6.3mg/L.The clearance of COD is 98.8%.
The cupric oxide product cupric oxide content that the present embodiment prepares is 99.3%, and chloride content is 18ppm.
Embodiment 3
Microetch waste liquid and bluestone waste utilize a method, comprise the following steps:
S1. preparation mixes contained waste liquid: microetch waste liquid 4500mL and the cupric 8.0g/L of sulfuric acid-hydrogen peroxide system of cupric 8.5g/L, hydrogen peroxide 16mL/L, COD5063mg/L, the bluestone waste 750mL of ferrous 2.6g/L, COD1143mg/L are mixed, obtain mixing contained waste liquid 5250mL;
S2. removing COD and copper iron separates: 715mL30% sodium hydrogen carbonate solution is slowly added and mixed in contained waste liquid, make the pH value of system 3.2, add the ironic hydroxide of 15g and the hydrogen peroxide that 390mL massfraction is 27.5%, stir 1h, adding 1.0mL mass concentration is 0.1% non-ionic polyacrylamide again, stirs 10 minutes, filters, rinsing solid phase 3 times, use 20mL water rinse, gained suction filtration liquid and rinse water to be mixed to get cupric acid solution 6430mL at every turn; The main solid phase residue weight containing ironic hydroxide after rinsing is 17g;
S3. prepare cupric oxide:
S31. join alkali: 400g sodium hydroxide and 120g sodium carbonate, 80g sodium bicarbonate, it is 30% mixed alkali liquor that 1400mL is made into concentration;
S32. prepare cupric oxide wet brilliant: as reaction mother liquor, control 85 ℃ of temperature with 1000mL cupric oxide mother liquor, add mixed alkali liquor described in cupric acid solution described in step S2 and step S31, control pH value 11.0, react 2 hours, obtain the wet crystal 79g of cupric oxide;
S33. filtration, the wet crystal of rinsing cupric oxide 3 times are used 100mL water rinse at every turn; After dry, with 500 ℃ of roastings 1 hour, obtain plating-grade copper oxide crystal 58g;
S34. the suction filtration liquid of cupric oxide is mixed with rinse water, obtain mixed solution 7910mL, after precipitation, first spent ion exchange resin is removed wherein remaining cupric ion, make it lower than 0.5mg/L, by concentrating under reduced pressure crystallization, obtain technical grade sal glauberi again, the water after transpiration cooling can be back to production.
The cupric acid solution COD that the present embodiment step S2 makes is 28mg/L, copper content 8.3g/L, iron level 5.9mg/L.The clearance of COD is 99%.
The cupric oxide product cupric oxide content that the present embodiment prepares is 99.2%, and chloride content is 19ppm.
Embodiment 4
S1, S2 and S3 are with embodiment 1;
S4. prepare copper sulfate: use 200ml clear water as mother liquor, add the wet crystal 66g of the cupric oxide after rinsing in step S33, with cupric oxide described in 28.5mL concentrated sulfuric acid dissolution, regulating pH value is 1.5, control 85 ℃ of temperature, react to degree Beaume and reach 42, then by reaction solution suction filtration, crystallisation by cooling, spend 10ml ionized water and get express developed, after drying, obtain cupric sulfate purified 84g.
The copper sulfate product copper sulfate content that the present embodiment prepares is 99.1%, and chloride content is 8ppm.
Embodiment 5
S1, S2 and S3 are with embodiment 2;
S4. prepare copper sulfate: use 200ml copper sulfate mother liquor as mother liquor, add the wet crystal 55g of the cupric oxide after rinsing in step S33, with cupric oxide described in 22mL concentrated sulfuric acid dissolution, regulating pH value is 1.8, control 90 ℃ of temperature, react to degree Beaume and reach 43.5, then suction filtration, crystallisation by cooling, spend 20ml ionized water and get express developed, after drying, obtain cupric sulfate purified 165g.
The copper sulfate product copper sulfate content that the present embodiment prepares is 99.3%, and chloride content is 12ppm.
Embodiment 6
S1, S2 and S3 are with embodiment 3;
S4. prepare copper sulfate: use 200ml copper sulfate mother liquor as mother liquor, add the wet crystal 47g of the cupric oxide after rinsing in step S33, with cupric oxide described in 23mL concentrated sulfuric acid dissolution, regulating pH value is 2.0, control 100 ℃ of temperature, react to degree Beaume and reach 45, then suction filtration, crystallisation by cooling, spend 20ml ionized water and get express developed, after drying, obtain cupric sulfate purified 145g.
The copper sulfate product copper sulfate content that the present embodiment prepares is 99.2%, and chloride content is 10ppm.
Embodiment 7
S1. preparation mixes contained waste liquid: the microetch waste liquid 400mL of sulfuric acid-Sodium Persulfate system of microetch waste liquid 3600mL and the cupric 8.7g/L of sulfuric acid-hydrogen peroxide system of cupric 9.0g/L, hydrogen peroxide 10mL/L, COD3542mg/L, Sodium Persulfate 7g/L, COD3679mg/L is mixed, mix with the bluestone waste 1000mL of cupric 9.4g/L, ferrous 2.1g/L, COD2211mg/L again, obtain mixing contained waste liquid 5000mL;
S2. removing COD and copper iron separates: 280g powdered sodium carbonate is slowly added and mixed in contained waste liquid, make the pH value of system 2.5, add the ironic hydroxide of 25g and the hydrogen peroxide that 405mL massfraction is 27.5%, stir 1h, adding 0.5mL mass concentration is 0.1% cationic-type polyacrylamide again, and stirring reaction 5 minutes filters, rinsing solid phase 2 times, use 50mL water rinse, gained suction filtration liquid and rinse water to be mixed to get cupric acid solution 5500mL at every turn; The main solid phase residue weight containing ironic hydroxide after rinsing is 35g.
In the present embodiment step S2, the cupric acid solution COD making is 14mg/L, copper content 9.1g/L, iron level 7.1mg/L.The clearance of COD is 99.5%.
Embodiment 8
S1. preparation mixes contained waste liquid: the microetch waste liquid 200mL of sulfuric acid-Sodium Persulfate system of microetch waste liquid 3800mL and the cupric 10.0g/L of sulfuric acid-hydrogen peroxide system of cupric 10.0g/L, hydrogen peroxide 8mL/L, COD4156mg/L, Sodium Persulfate 5g/L, COD3986mg/L is mixed, mix with the bluestone waste 800mL of cupric 10.0g/L, ferrous 3.1g/L, COD1569mg/L again, obtain mixing contained waste liquid 4800mL;
S2. removing COD and copper iron separates: 333mL50% sodium hydroxide solution is slowly added and mixed in contained waste liquid, make the pH value of system 3.0, add the ironic hydroxide of 16g and the hydrogen peroxide that 239mL massfraction is 35%, stir 1h, adding 1.5mL mass concentration is 0.1% anion-polyacrylamide again, and stirring reaction 8 minutes filters, rinsing solid phase 3 times, use 25mL water rinse, gained suction filtration liquid and rinse water to be mixed to get cupric acid solution 5480mL at every turn; The main solid phase residue weight containing ironic hydroxide after rinsing is 24g.
In the present embodiment step S2, the cupric acid solution COD making is 19mg/L, copper content 10.0g/L, iron level 6.8mg/L.The clearance of COD is 99.2%.
Embodiment 9
A treatment process for microetch waste liquid and bluestone waste, comprises the following steps:
S1. preparation mixes contained waste liquid: the microetch waste liquid 300mL of sulfuric acid-Sodium Persulfate system of microetch waste liquid 4200mL and the cupric 9.1g/L of sulfuric acid-hydrogen peroxide system of cupric 8.5g/L, hydrogen peroxide 16mL/L, COD5063mg/L, Sodium Persulfate 8.8g/L, COD5633mg/L is mixed, mix with the bluestone waste 750mL of cupric 8.0g/L, ferrous 2.6g/L, COD1143mg/L again, obtain mixing contained waste liquid 5250mL;
S2. removing COD and copper iron separates: 710mL30% sodium hydrogen carbonate solution is slowly added and mixed in contained waste liquid, make the pH value of system 3.2, add the ironic hydroxide of 11g and the hydrogen peroxide that 378mL massfraction is 27.5%, stir 1h, adding 1.0mL mass concentration is 0.1% non-ionic polyacrylamide again, stirs 10 minutes, filters, rinsing solid phase 3 times, use 20mL water rinse, gained suction filtration liquid and rinse water to be mixed to get cupric acid solution 6380mL at every turn; The main solid phase residue weight containing ironic hydroxide after rinsing is 17g.
The cupric acid solution COD that the present embodiment step S2 makes is 12mg/L, copper content 8.5g/L, iron level 7.0mg/L.The clearance of COD is 99.6%.
Comparative example 1
S1 is with embodiment 1;
Other step of S2, with embodiment 1, is not just added hydrogen peroxide;
S3 and S4 are with embodiment 1
The cupric acid solution COD that this comparative example step S2 makes is 1567mg/L, copper content 8.0g/L, iron level 256mg/L.
The cupric oxide product cupric oxide content that this comparative example prepares is 96%, and chloride content is 100ppm.
Comparative example 2
S1, S2 are with embodiment 1;
Other step of S3, with embodiment 1, is just synthesized cupric oxide at 30 ℃ or 100 ℃;
S4 is with embodiment 1;
The cupric oxide product cupric oxide content that this comparative example prepares is 95%, and chloride content is 2750ppm.
Comparative example 3
S1, S2 are with embodiment 1;
Other step of S3 is with embodiment 1, is just synthetic cupric oxide under 6.0 or 11.5 condition at pH;
S4 is with embodiment 1;
The cupric oxide product cupric oxide content that this comparative example prepares is 95%, and chloride content is 3600ppm.
Comparative example 4
S1, S2, S3 are with embodiment 4;
Other step of S4, with embodiment 4, is just adjusted to 39 by degree Beaume;
The copper sulfate product crystallization velocity that this comparative example prepares is excessively slow, and particle is large, when use, will pulverize, and copper sulfate content is 99%, and chloride content is 20ppm.
Comparative example 5
S1, S2, S3 are with embodiment 4;
Other step of S4, with embodiment 4, is just adjusted to 48 by degree Beaume;
The copper sulfate product crystallization velocity that this comparative example prepares is too fast, and particle is partially thin, and copper sulfate content is 98%, and chloride content is 200ppm.
Claims (8)
1. a treatment process for microetch waste liquid and bluestone waste, is characterized in that, comprises the following steps:
S1. preparation mixes contained waste liquid: the microetch waste liquid of sulfuric acid-hydrogen peroxide system is mixed with bluestone waste, obtain mixing contained waste liquid, make to mix copper content 7 ~ 10g/L in contained waste liquid, iron level 0.3 ~ 1g/L, COD content 2000 ~ 4000mg/L, hydrogen peroxide content 0.5 ~ 5mL/L;
S2. removing COD and copper iron separates: regulate the pH value of mixing contained waste liquid 2.5 ~ 3.2, add the ironic hydroxide of 20 ~ 50g and the hydrogen peroxide that is 18 ~ 24g by significant quantity calculated mass by every L mixing contained waste liquid, and stirring reaction 1 ~ 3 hour, then add coagulant aids; After completion of the reaction, filter, collect solid formation, rinsing solid formation 2 ~ 3 times, and collect filtrate and float scrub raffinate.
2. the treatment process of microetch waste liquid and bluestone waste according to claim 1, it is characterized in that, S1. in, the microetch waste liquid of the microetch waste liquid of sulfuric acid-hydrogen peroxide system, sulfuric acid-Sodium Persulfate system is mixed with bluestone waste, obtain mixing contained waste liquid, make to mix copper content 7 ~ 10g/L in contained waste liquid, iron level 0.3 ~ 1g/L, COD content 2000 ~ 4000mg/L, hydrogen peroxide content 0.5 ~ 5mL/L, persulfate content 0.2 ~ 1g/L.
3. adopt microetch waste liquid and bluestone waste to prepare a method for cupric oxide, it is characterized in that, comprise the steps:
First prepare filtrate and float the mixed solution of scrub raffinate according to step described in claim 1 or 2, then take this mixed solution as copper raw material, preparing cupric oxide.
4. adopt according to claim 3 microetch waste liquid and bluestone waste to prepare the method for cupric oxide, it is characterized in that, the described step of preparing cupric oxide is:
S31. join alkali: prepare mixed alkali liquor, described mixed alkali liquor is that highly basic and strong base-weak acid salt dissolve the aqueous solution obtaining; The mass ratio of described mixed alkali liquor strong base-weak acid salt and highly basic is 1:1 ~ 1:5, and described mixed alkali liquor mass concentration is 10 ~ 30%, and described highly basic is any one or its mixture in sodium hydroxide or potassium hydroxide; Described strong base-weak acid salt is any one or a few in sodium carbonate, salt of wormwood, sodium bicarbonate or saleratus;
S32. prepare cupric oxide wet brilliant: with clear water or cupric oxide mother liquor as reaction mother liquor, control temperature between 60 ~ 90 ℃, add mixed alkali liquor described in cupric acid solution described in step S2 and step S31, control pH value between 8.5 ~ 11.0, react 3 ~ 5 hours, obtain the wet crystal of cupric oxide;
S33. filtration, the wet crystal of rinsing cupric oxide 2 ~ 3 times;
S34. dry roasting, roasting oxidation copper; Described maturing temperature is 300 ~ 500 ℃, and roasting time is 1 ~ 2h.
5. adopt microetch waste liquid and bluestone waste to prepare a method for copper sulfate, it is characterized in that, comprise the steps:
First prepare filtrate and float the mixed solution of scrub raffinate according to step described in claim 1 or 2, then take this mixed solution as copper raw material, preparing copper sulfate.
6. adopt according to claim 5 microetch waste liquid and bluestone waste to prepare the method for copper sulfate, it is characterized in that, comprise the steps:
A. prepare the wet crystal of cupric oxide after rinsing according to method described in claim 4;
B. with clear water or copper sulfate mother liquor as mother liquor, add the wet crystal of cupric oxide after rinsing, with concentrated sulfuric acid dissolution, regulating pH value is 1.5 ~ 2.0,85 ~ 100 ℃ of control temperature are reacted, press filtration after completion of the reaction, crystallization, washing, obtain copper sulfate.
7. according to the method described in any one claim in claim 1 to 6, it is characterized in that, described in step S2, regulate and mix contained waste liquid for adding alkali or alkali lye to regulate.
8. according to the method described in any one claim in claim 1 to 6, it is characterized in that, in step S2, coagulant aids is polyacrylamide.
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| CN114684847B (en) * | 2020-12-25 | 2023-11-10 | 广州科城环保科技有限公司 | Copper hydroxide, preparation method and application thereof, and bactericide |
| CN113278976A (en) * | 2021-04-27 | 2021-08-20 | 南昌航空大学 | Clean production process for etching aluminum and aluminum alloy |
| CN114702058A (en) * | 2022-04-25 | 2022-07-05 | 惠州市东江环保技术有限公司 | Process for comprehensively recycling micro-etching waste liquid |
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