CN106495205B - A kind of cupric sulfate purified and its production technology - Google Patents
A kind of cupric sulfate purified and its production technology Download PDFInfo
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- CN106495205B CN106495205B CN201611016408.3A CN201611016408A CN106495205B CN 106495205 B CN106495205 B CN 106495205B CN 201611016408 A CN201611016408 A CN 201611016408A CN 106495205 B CN106495205 B CN 106495205B
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- 229910000366 copper(II) sulfate Inorganic materials 0.000 title claims abstract description 48
- 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 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- 238000005516 engineering process Methods 0.000 title claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 154
- 239000002699 waste material Substances 0.000 claims abstract description 136
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 130
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 130
- 238000001914 filtration Methods 0.000 claims abstract description 106
- 238000000746 purification Methods 0.000 claims abstract description 84
- 238000005530 etching Methods 0.000 claims abstract description 57
- 238000002425 crystallisation Methods 0.000 claims abstract description 19
- 230000008025 crystallization Effects 0.000 claims abstract description 19
- 238000005342 ion exchange Methods 0.000 claims abstract description 16
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 14
- 238000000605 extraction Methods 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 239000000706 filtrate Substances 0.000 claims description 87
- 239000012065 filter cake Substances 0.000 claims description 66
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 47
- 239000002253 acid Substances 0.000 claims description 43
- 239000003795 chemical substances by application Substances 0.000 claims description 34
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 30
- 241000370738 Chlorion Species 0.000 claims description 29
- 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 22
- 239000012452 mother liquor Substances 0.000 claims description 22
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 21
- 230000002378 acidificating effect Effects 0.000 claims description 21
- 239000000908 ammonium hydroxide Substances 0.000 claims description 21
- 239000000284 extract Substances 0.000 claims description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000012535 impurity Substances 0.000 claims description 15
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 15
- 239000003921 oil Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 14
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- 229910001424 calcium ion Inorganic materials 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 14
- 239000006259 organic additive Substances 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 7
- 239000008139 complexing agent Substances 0.000 claims description 7
- 238000005360 mashing Methods 0.000 claims description 7
- 229920002401 polyacrylamide Polymers 0.000 claims description 7
- 239000008399 tap water Substances 0.000 claims description 7
- 235000020679 tap water Nutrition 0.000 claims description 7
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000011814 protection agent Substances 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 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 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 238000004064 recycling Methods 0.000 abstract description 8
- 239000002912 waste gas Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000010842 industrial wastewater Substances 0.000 abstract description 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 210000002249 digestive system Anatomy 0.000 abstract 1
- 244000144977 poultry Species 0.000 abstract 1
- 150000002500 ions Chemical group 0.000 description 9
- 230000000694 effects Effects 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000003472 neutralizing effect Effects 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- UGWKCNDTYUOTQZ-UHFFFAOYSA-N copper;sulfuric acid Chemical compound [Cu].OS(O)(=O)=O UGWKCNDTYUOTQZ-UHFFFAOYSA-N 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/10—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The present invention relates to industrial waste water treatment, and in particular to a kind of cupric sulfate purified and its production technology, the production technology include the following steps：A, the slightly preparation of purification etching waste liquor；B, neutralization and press filtration；C, extraction and ion exchange；D, acidifying and crystallization；E, purification and crystallization.The production technology of the present invention is environment friendly and pollution-free, and no waste gas and wastes discharge, realizes waste utilization, mother liquid recycling, Zi Yehuishou enterprises, high financial profit, and equipment is simple, easy to operate.Content of copper ion in cupric sulfate purified produced by the present invention is up to 98%, is beneficial to the digestive system for improving poultry.
Description
Technical field
The present invention relates to industrial waste water treatment, and in particular to a kind of cupric sulfate purified and its production technology.
Background technology
At present, the cupric sulfate purified as electroplating additive is given birth to by raw material of wiring board copper-containing etching waste solution
Production, copper-containing etching waste solution has two kinds of acid waste liquid and alkaline waste liquor.And traditional copper sulphate production technology is without purification, system
The copper sulphate crude product quality obtained is not up to standard, containing more impurity and metal ion, in addition, the tail water produced in production cannot be again
It is raw, cause to waste, discharge also results in environmental pollution.
The content of the invention
In order to overcome shortcoming and defect existing in the prior art, it is an object of the invention to provide one kind to electroplate level sulfuric acid
The production technology of copper, the production process equipment is simple, easy to operate, environment friendly and pollution-free, and no waste gas and wastes discharge, realizes waste profit
With, mother liquid recycling, Zi Yehuishou enterprises, high financial profit.
Another object of the present invention is to provide a kind of cupric sulfate purified, the content of copper ion in the cupric sulfate purified
Up to 98%, production cost is low.
The purpose of the present invention is achieved through the following technical solutions：A kind of production technology of cupric sulfate purified, including it is as follows
Step：
A, the slightly preparation of purification etching waste liquor：
The preparation of A1, thick purification acidic etching waste liquid：Cupric acidic etching waste liquid is subjected to coarse filtration, acid purification and mistake
Filter, is made thick purification acid waste liquid；
The preparation of A2, thick purification alkaline etching waste liquid for producing：Cupric alkaline etching waste liquid for producing is subjected to coarse filtration, alkalescence purification and mistake
Filter, is made thick purification alkaline waste liquor；
B, neutralization and press filtration：
B1, will made from step A1 slightly thick purification alkaline waste liquor made from purification acid waste liquid and step A2 neutralize it is anti-
Should, first time press filtration is then carried out, obtains first-time filtrate and a filter cake, and first-time filtrate is subjected to smart filtering；
B2, a filter cake for obtaining step B1 add water to be beaten, and then carry out second of press filtration, obtain secondary filtrate
With secondary filter cake；
C, extraction and ion exchange：
C1, extracted after the secondary filtrate that the first-time filtrate after step B1 essence filterings and step B2 obtain is mixed with AB oil
Take, obtain extract and waste liquid, extract is stripped with sulfuric acid, obtains anti-stripping agent；
First time ion exchange is carried out after C2, the waste liquid filtering for obtaining step C1, the A liquid of copper ions is obtained and is free of
The B liquid of copper ion；
C3, by the B liquid of the obtained not copper ions of step C2 add alkali to remove sulfate ion, then carries out second
Ion exchange, to remove calcium ion, obtains the sub- liquid of not copper ions and calcium ion；
D, acidifying and crystallization：
It is beaten after the secondary filter cake that the A liquid of the obtained copper ions of step C2 and the step B2 are obtained is mixed,
Acidifying, crystallization, obtains feed-grade bluestone and mother liquor；
Alternatively, by the obtained secondary filter cake of the A liquid of the obtained copper ions of step C2, the step B2 and the step C1
It is beaten, is acidified, crystallization, obtains feed-grade bluestone and mother liquor after obtained anti-stripping agent mixing；
E, purification and crystallization：
The obtained feed-grade bluestones of step D are dissolved in water, carry out impurity and purification, then heating concentration, crystallization, obtains
Cupric sulfate purified.
Preferably, the step A1 is specially：The acidic etching waste liquid that content of copper ion is 80-100g/L is carried out thick
Filter, coarse filtration mesh number is 300-500 mesh, content of copper ion is reduced to 70-80g/L, and the filtrate after coarse filtration is added acid purification
In tank, sodium chlorate is added, adjusting pH to 4.5-5.5 with ammonium hydroxide and tap water carries out acid purification, then filters, and is made thick net
Change acid waste liquid.The present invention by strictly controlling the adjusting of coarse filtration mesh number and pH, can remove sandstone impurity in acid waste liquid and
The impurity metal ions such as iron, arsenic, reach preferable filtration, purification effect.
Preferably, in the step A1, the content of copper ion is 80-100g/L in acidic etching waste liquid, and chlorion contains
Measure as 180-200g/L, the content of organic additive is 0.1-1.0g/L, and the mass concentration of HCl is 4.2-4.5%；Organic addition
Agent determines agent, complexing agent and shore protection agent including ammonia, its weight ratio is 2-4:4-6:6-8；The dosage of sodium chlorate is 8-12g/L.This hair
Bright component and its weight ratio by strictly controlling organic additive, and the dosage of control sodium chlorate, can effectively remove sandstone
Impurity and impurity metal ion, improve purification efficiency and clean-up effect, and the impurity of obtained thick purification acidic etching waste liquid is less.
Preferably, the step A2 is specially：By the alkaline etching waste liquid for producing ammonium hydroxide that content of copper ion is 100-120g/L
Adjusting pH is 9.8-10.0, carries out coarse filtration, and coarse filtration mesh number is 300-500 mesh, content of copper ion is reduced to 90-110g/L, will
Filtrate after coarse filtration is added in alkaline purification pot, adds magnesium chloride, and adjusting pH to 7-8 with ammonium hydroxide and polyacrylamide carries out alkali
Property purification, then filter, thick purification alkaline waste liquor be made.Adjusting of the invention by strictly controlling coarse filtration mesh number and pH, can go
Except impurity metal ions such as the sandstone impurity in alkaline waste liquor and iron, arsenic, reach preferable filtration, purification effect.
Preferably, in the step A2, the content of copper ion is 100-120g/L in alkaline etching waste liquid for producing, and chlorion contains
Measure as 160-200g/L；The dosage of magnesium chloride is 8-12g/L.Dosage of the invention by strictly controlling magnesium chloride, can effectively go
Except sandstone impurity and impurity metal ion, purification efficiency and clean-up effect are improved, it is obtained slightly to purify the miscellaneous of alkaline etching waste liquid for producing
Matter is less.
Preferably, the step B1 is specially：It is thick made from acid waste liquid and step A2 by slightly being purified made from step A1
Alkaline waste liquor is purified by weight 0.8-1.2:1 carries out neutralization reaction, obtains reaction solution, adjusts the pH to 6-7 of reaction solution, then
First time press filtration is carried out, press filtration mesh number is 80-100 mesh, obtains first-time filtrate and a filter cake, and first-time filtrate is carried out smart mistake
Filter；
Wherein, the content of copper ion is 3-5g/L in first-time filtrate, and the content of chlorion is 80-90g/L；In filter cake
The content of copper ion is 250-300kg/m3.The present invention is by strictly controlling slightly purification acid waste liquid and thick purification in neutralization reaction
The weight ratio of alkaline waste liquor and the pH of reaction solution, can make neutralization reaction more abundant, promote the generation precipitated in waste liquid, to go to clean
Matter；It is 80-100 mesh by strictly controlling press filtration mesh number, and smart filtering is carried out to first-time filtrate, can more effectively removes reaction solution
The sediment of middle generation and remaining fine impurities, improve the effect of filtration, purification.
Preferably, the step B2 is specially：The filter cake that step B1 is obtained adds water to be by weight 1.3-1.7:1
It is beaten after mixing, then carries out second of press filtration, obtains secondary filtrate and secondary filter cake；
Wherein, the content of copper ion is 0.2-0.5g/L in secondary filtrate, and the content of chlorion is 14-18g/L；Secondary filter
The content of copper ion is 250-300kg/m in cake3.Mixed weight ratio of the invention by strictly controlling a filter cake and water, energy
A small amount of remaining chlorion is effectively removed, improves purifying rate.
Preferably, the step C1 is specially：First-time filtrate after step B1 essence filterings and step B2 are obtained secondary
Filtrate mixes, and obtains the mixing filtrate that content of copper ion is 3-7g/L, is extracted with AB oil, obtain extract and waste liquid, will
Extract is stripped with sulfuric acid, is repeatedly extracted and is stripped, and obtains the back extraction that content of copper ion is 40-45g/L
Liquid.A is MTDC6 in the AB oil that the present invention uses, and B is MTD8, its volume ratio 1:3-4, both are oily, the waste liquids with copper ions
Split-phase shunting is stripped work so as to be extracted after agitation.The AB oil costs of material that the present invention uses are low, are currently on the market
20% or so of the cost of existing AB oil, substantially reduces the cost of material of copper sulphate production technology.AB oil be no sulfate liquid into
Row extraction, is having sulfate liquid to carry out back extraction release copper ion, and the present invention makees by using AB oil as extractant, sulfuric acid
For strippant, the extraction yield of copper ion in filtrate can be greatly improved, and by extraction and back extraction repeatedly, is obtained
The anti-stripping agent of higher copper ion concentration.
The step C2 is specially：After the waste liquid filtering that step C1 is obtained, add dilute sulfuric acid and carry out the first secondary ion friendship
Change, obtain the A liquid of copper ions and the B liquid of non-copper ions.The present invention is by the way that waste liquid is filtered, to remove impurity, and
Ion exchange is carried out using dilute sulfuric acid, copper ion can be thoroughly removed, to obtain the B liquid of the A liquid of copper ions and non-copper ions.
The step C3 is specially：By the B liquid of the obtained not copper ions of step C2 add calcium hydroxide or calcium chloride with
Sulfate ion is removed, second of ion exchange is then carried out, to remove calcium ion, obtains the son of not copper ions and calcium ion
Liquid.The present invention can thoroughly remove sulfate ion by using calcium hydroxide or calcium chloride, and by second of ion exchange,
The calcium ion of addition can be thoroughly removed, to obtain the sub- liquid of not copper ions and calcium ion, can return and sell to circuit board etching enterprise
Circuit board etching processing is carried out, achievees the purpose that recycling, it is with good economic efficiency.
Preferably, the step D is specially：The A liquid of the obtained copper ions of step C2 and the step B2 are obtained
It is beaten after secondary filter cake mixing, adds the concentrated sulfuric acid that mass concentration is 95-99% and be acidified, then crystallized, through separation
After obtain cupric sulfate purified and mother liquor.
Alternatively, the step D is specially：The A liquid of the obtained copper ions of step C2, the step B2 are obtained secondary
Be beaten after the mixing of anti-stripping agent that filter cake and the step C1 are obtained, add the concentrated sulfuric acid that mass concentration is 95-99% into
Row acidifying, then crystallizes, cupric sulfate purified and mother liquor is obtained after separation.The present invention by using copper ions A liquid, two
Secondary filter cake and anti-stripping agent, and the mass concentration of the concentrated sulfuric acid is strictly controlled, the content of copper ion of obtained feed-grade bluestone is high,
And obtained mother liquor can introduce neutralizing tank reuse, mother liquid recycling is realized, environment friendly and pollution-free, no waste liquid discharge.
Another object of the present invention is achieved through the following technical solutions：A kind of cupric sulfate purified, the plating level sulfuric acid
Copper is made according to production technology described above.
The beneficial effects of the present invention are：The production process equipment of the present invention is simple, easy to operate, environment friendly and pollution-free, nothing
Waste gas and wastes are discharged, and realize waste utilization, mother liquid recycling, Zi Yehuishou enterprises, high financial profit.
The production technology of the present invention is become by the way that etching waste liquor waste utilization, the copper sulphate of generation, sub- liquid can be sold
Waste be changed into values, and the cost of etching waste liquor is 2000 yuan/ton, and the sub- liquid of recycling is 600-700 yuan/ton, the price of cupric sulfate purified
For 13000 yuan/ton or so, high financial profit.
The production technology environmental protection of the present invention, contamination-free discharge, is specially：（1）Formed in cupric acidic etching waste liquid
The organic substance such as the ammonia formed and the acid mist gas formed in neutralizing tank and ammonia in acid mist gas, cupric alkaline etching waste liquid for producing
Enter exhaust gas tower and carry out purified treatment, no exhaust gas discharge；（2）The sub- liquid that waste liquid is formed after purified treatment can be attached as having
Value added sale of finished goods is used to circuit board etching producer, is turned waste into wealth；（3）The dope formed during extraction can be used for secondary filter cake
Mashing processing, and the mother liquor that produces can be back to use in neutralizing tank after crystallization tank crystallization, no waste liquid discharge.
Content of copper ion in cupric sulfate purified produced by the present invention is up to 98%, and production cost is low.
Embodiment
For the ease of the understanding of those skilled in the art, with reference to embodiment, the present invention is further illustrated, real
The content that the mode of applying refers to not is limitation of the invention.
Embodiment 1
A kind of production technology of feed-grade bluestone, includes the following steps：
A, the slightly preparation of purification etching waste liquor：
The preparation of A1, thick purification acidic etching waste liquid：Cupric acidic etching waste liquid is subjected to coarse filtration, acid purification and mistake
Filter, is made thick purification acid waste liquid；
The preparation of A2, thick purification alkaline etching waste liquid for producing：Cupric alkaline etching waste liquid for producing is subjected to coarse filtration, alkalescence purification and mistake
Filter, is made thick purification alkaline waste liquor；
B, neutralization and press filtration：
B1, will made from step A1 slightly thick purification alkaline waste liquor made from purification acid waste liquid and step A2 neutralize it is anti-
Should, first time press filtration is then carried out, obtains first-time filtrate and a filter cake, and first-time filtrate is subjected to smart filtering；
B2, a filter cake for obtaining step B1 add water to be beaten, and then carry out second of press filtration, obtain secondary filtrate
With secondary filter cake；
C, extraction and ion exchange：
C1, extracted after the secondary filtrate that the first-time filtrate after step B1 essence filterings and step B2 obtain is mixed with AB oil
Take, obtain extract and waste liquid, extract is stripped with sulfuric acid, obtains anti-stripping agent；
First time ion exchange is carried out after C2, the waste liquid filtering for obtaining step C1, the A liquid of copper ions is obtained and is free of
The B liquid of copper ion；
C3, by the B liquid of the obtained not copper ions of step C2 add alkali to remove sulfate ion, then carries out second
Ion exchange, to remove calcium ion, obtains the sub- liquid of not copper ions and calcium ion；
D, acidifying and crystallization：
It is beaten after the secondary filter cake that the A liquid of the obtained copper ions of step C2 and the step B2 are obtained is mixed,
Acidifying, crystallization, obtains feed-grade bluestone and mother liquor；
Alternatively, by the obtained secondary filter cake of the A liquid of the obtained copper ions of step C2, the step B2 and the step C1
It is beaten, is acidified, crystallization, obtains feed-grade bluestone and mother liquor after obtained anti-stripping agent mixing；
E, purification and crystallization：
The obtained feed-grade bluestones of step D are dissolved in water, carry out impurity and purification, then heating concentration, crystallization, obtains
Cupric sulfate purified.
The step A1 is specially：The acidic etching waste liquid that content of copper ion is 80g/L is subjected to coarse filtration, coarse filtration mesh number is
300 mesh, make content of copper ion be reduced to 70g/L, and the filtrate after coarse filtration is added in acid purification pot, adds sodium chlorate, is used
Ammonium hydroxide and tap water adjust pH to 4.5 and carry out acid purification, then filter, and thick purification acid waste liquid is made.
In the step A1, the content of copper ion is 80g/L in acidic etching waste liquid, and the content of chlorion is 180g/L,
The content of organic additive is 0.1g/L, and the mass concentration of HCl is 4.2%；Organic additive determines agent, complexing agent and shield including ammonia
Bank agent, its weight ratio are 2:4:6；The dosage of sodium chlorate is 8g/L.
The step A2 is specially：It is 9.8 that the alkaline etching waste liquid for producing that content of copper ion is 100g/L is adjusted pH with ammonium hydroxide,
Coarse filtration is carried out, coarse filtration mesh number is 300 mesh, content of copper ion is reduced to 90g/L, and the filtrate after coarse filtration is added alkaline purification pot
In, magnesium chloride is added, adjusting pH to 7 with ammonium hydroxide and polyacrylamide carries out alkaline purification, then filters, thick Purification of alkali is made
Property waste liquid.
In the step A2, the content of copper ion is 100g/L in alkaline etching waste liquid for producing, and the content of chlorion is 160g/L；
The dosage of magnesium chloride is 8g/L.
The step B1 is specially：Thick purification alkalescence made from acid waste liquid and step A2 will be slightly purified made from step A1
Waste liquid is by weight 0.8:1 carries out neutralization reaction, obtains reaction solution, adjusts the pH to 6 of reaction solution, then carries out first time pressure
Filter, press filtration mesh number is 80 mesh, obtains first-time filtrate and a filter cake, and first-time filtrate is carried out smart filtering；
Wherein, the content of copper ion is 3g/L in first-time filtrate, and the content of chlorion is 80g/L；In filter cake copper from
The content of son is 250kg/m3。
The step B2 is specially：The filter cake that step B1 is obtained adds water to be 1.3 by weight:Carried out after 1 mixing
Mashing, then carries out second of press filtration, obtains secondary filtrate and secondary filter cake；
Wherein, the content of copper ion is 0.2g/L in secondary filtrate, and the content of chlorion is 14g/L；Copper in secondary filter cake
The content of ion is 250kg/m3。
The step C1 is specially：The secondary filtrate that first-time filtrate after step B1 essence filterings and step B2 obtain is mixed
Close, obtain the mixing filtrate that content of copper ion is 3g/L, extracted with AB oil, obtain extract and waste liquid, extract is used
Sulfuric acid is stripped, and is repeatedly extracted and is stripped, and obtains the anti-stripping agent that content of copper ion is 40g/L；
The step C2 is specially：After the waste liquid filtering that step C1 is obtained, add dilute sulfuric acid and carry out the first secondary ion friendship
Change, obtain the A liquid of copper ions and the B liquid of non-copper ions；
The step C3 is specially：By the B liquid of the obtained not copper ions of step C2 add calcium hydroxide or calcium chloride with
Sulfate ion is removed, second of ion exchange is then carried out, to remove calcium ion, obtains the son of not copper ions and calcium ion
Liquid.
The step D is specially：The secondary filter cake that the A liquid of the obtained copper ions of step C2 and the step B2 are obtained
It is beaten after mixing, adds the concentrated sulfuric acid that mass concentration is 95% and be acidified, then crystallize, feed is obtained after separation
Grade bluestone and mother liquor；
Alternatively, the step D is specially：The A liquid of the obtained copper ions of step C2, the step B2 are obtained secondary
It is beaten after the anti-stripping agent mixing that filter cake and the step C1 are obtained, adds the concentrated sulfuric acid that mass concentration is 95% and carry out
Acidifying, then crystallizes, feed-grade bluestone and mother liquor is obtained after separation.
A kind of feed-grade bluestone, the feed-grade bluestone are made according to above-mentioned production technology.
Embodiment 2
The present embodiment and above-described embodiment 1 difference lies in：
The step A1 is specially：The acidic etching waste liquid that content of copper ion is 85g/L is subjected to coarse filtration, coarse filtration mesh number is
350 mesh, make content of copper ion be reduced to 72g/L, and the filtrate after coarse filtration is added in acid purification pot, adds sodium chlorate, is used
Ammonium hydroxide and tap water adjust pH to 4.8 and carry out acid purification, then filter, and thick purification acid waste liquid is made.
In the step A1, the content of copper ion is 85g/L in acidic etching waste liquid, and the content of chlorion is 185g/L,
The content of organic additive is 0.3g/L, and the mass concentration of HCl is 4.3%；Organic additive determines agent, complexing agent and shield including ammonia
Bank agent, its weight ratio are 2:4:6；The dosage of sodium chlorate is 9g/L.
The step A2 is specially：It is 9.8 that the alkaline etching waste liquid for producing that content of copper ion is 105g/L is adjusted pH with ammonium hydroxide,
Coarse filtration is carried out, coarse filtration mesh number is 350 mesh, content of copper ion is reduced to 95g/L, and the filtrate after coarse filtration is added alkaline purification pot
In, magnesium chloride is added, adjusting pH to 7.2 with ammonium hydroxide and polyacrylamide carries out alkaline purification, then filters, thick purification is made
Alkaline waste liquor.
In the step A2, the content of copper ion is 105g/L in alkaline etching waste liquid for producing, and the content of chlorion is 170g/L；
The dosage of magnesium chloride is 9g/L.
The step B1 is specially：Thick purification alkalescence made from acid waste liquid and step A2 will be slightly purified made from step A1
Waste liquid is by weight 0.9:1 carries out neutralization reaction, obtains reaction solution, adjusts the pH to 6.2 of reaction solution, then carries out first time pressure
Filter, press filtration mesh number is 85 mesh, obtains first-time filtrate and a filter cake, and first-time filtrate is carried out smart filtering；
Wherein, the content of copper ion is 3.5g/L in first-time filtrate, and the content of chlorion is 82g/L；Copper in filter cake
The content of ion is 260kg/m3。
The step B2 is specially：The filter cake that step B1 is obtained adds water to be 1.4 by weight:Carried out after 1 mixing
Mashing, then carries out second of press filtration, obtains secondary filtrate and secondary filter cake；
Wherein, the content of copper ion is 0.3g/L in secondary filtrate, and the content of chlorion is 15g/L；Copper in secondary filter cake
The content of ion is 260kg/m3。
The step C1 is specially：The secondary filtrate that first-time filtrate after step B1 essence filterings and step B2 obtain is mixed
Close, obtain the mixing filtrate that content of copper ion is 4g/L, extracted with AB oil, obtain extract and waste liquid, extract is used
Sulfuric acid is stripped, and is repeatedly extracted and is stripped, and obtains the anti-stripping agent that content of copper ion is 41g/L；
The step D is specially：The secondary filter cake that the A liquid of the obtained copper ions of step C2 and the step B2 are obtained
It is beaten after mixing, adds the concentrated sulfuric acid that mass concentration is 96% and be acidified, then crystallize, feed is obtained after separation
Grade bluestone and mother liquor；
Alternatively, the step D is specially：The A liquid of the obtained copper ions of step C2, the step B2 are obtained secondary
It is beaten after the anti-stripping agent mixing that filter cake and the step C1 are obtained, adds the concentrated sulfuric acid that mass concentration is 96% and carry out
Acidifying, then crystallizes, feed-grade bluestone and mother liquor is obtained after separation.
Embodiment 3
The present embodiment and above-described embodiment 1 difference lies in：
The step A1 is specially：The acidic etching waste liquid that content of copper ion is 90g/L is subjected to coarse filtration, coarse filtration mesh number is
400 mesh, make content of copper ion be reduced to 75g/L, and the filtrate after coarse filtration is added in acid purification pot, adds sodium chlorate, is used
Ammonium hydroxide and tap water adjust pH to 5.0 and carry out acid purification, then filter, and thick purification acid waste liquid is made.
In the step A1, the content of copper ion is 90g/L in acidic etching waste liquid, and the content of chlorion is 190g/L,
The content of organic additive is 0.5g/L, and the mass concentration of HCl is 4.3%；Organic additive determines agent, complexing agent and shield including ammonia
Bank agent, its weight ratio are 3:5:7；The dosage of sodium chlorate is 10g/L.
The step A2 is specially：It is 9.9 that the alkaline etching waste liquid for producing that content of copper ion is 110g/L is adjusted pH with ammonium hydroxide,
Coarse filtration is carried out, coarse filtration mesh number is 400 mesh, content of copper ion is reduced to 100g/L, and the filtrate after coarse filtration is added alkalescence purification
In tank, magnesium chloride is added, adjusting pH to 7.5 with ammonium hydroxide and polyacrylamide carries out alkaline purification, then filters, and is made thick net
Change alkaline waste liquor.
In the step A2, the content of copper ion is 110g/L in alkaline etching waste liquid for producing, and the content of chlorion is 180g/L；
The dosage of magnesium chloride is 10g/L.
The step B1 is specially：Thick purification alkalescence made from acid waste liquid and step A2 will be slightly purified made from step A1
Waste liquid is by weight 1:1 carries out neutralization reaction, obtains reaction solution, adjusts the pH to 6.5 of reaction solution, then carries out first time pressure
Filter, press filtration mesh number is 90 mesh, obtains first-time filtrate and a filter cake, and first-time filtrate is carried out smart filtering；
Wherein, the content of copper ion is 4g/L in first-time filtrate, and the content of chlorion is 85g/L；In filter cake copper from
The content of son is 270kg/m3。
The step B2 is specially：The filter cake that step B1 is obtained adds water to be 1.5 by weight:Carried out after 1 mixing
Mashing, then carries out second of press filtration, obtains secondary filtrate and secondary filter cake；
Wherein, the content of copper ion is 0.3g/L in secondary filtrate, and the content of chlorion is 16g/L；Copper in secondary filter cake
The content of ion is 270kg/m3。
The step C1 is specially：The secondary filtrate that first-time filtrate after step B1 essence filterings and step B2 obtain is mixed
Close, obtain the mixing filtrate that content of copper ion is 5g/L, extracted with AB oil, obtain extract and waste liquid, extract is used
Sulfuric acid is stripped, and is repeatedly extracted and is stripped, and obtains the anti-stripping agent that content of copper ion is 43g/L；
The step D is specially：The secondary filter cake that the A liquid of the obtained copper ions of step C2 and the step B2 are obtained
It is beaten after mixing, adds the concentrated sulfuric acid that mass concentration is 97% and be acidified, then crystallize, feed is obtained after separation
Grade bluestone and mother liquor；
Alternatively, the step D is specially：The A liquid of the obtained copper ions of step C2, the step B2 are obtained secondary
It is beaten after the anti-stripping agent mixing that filter cake and the step C1 are obtained, adds the concentrated sulfuric acid that mass concentration is 97% and carry out
Acidifying, then crystallizes, feed-grade bluestone and mother liquor is obtained after separation.
Embodiment 4
The present embodiment and above-described embodiment 1 difference lies in：
The step A1 is specially：The acidic etching waste liquid that content of copper ion is 95g/L is subjected to coarse filtration, coarse filtration mesh number is
450 mesh, make content of copper ion be reduced to 78g/L, and the filtrate after coarse filtration is added in acid purification pot, adds sodium chlorate, is used
Ammonium hydroxide and tap water adjust pH to 5.3 and carry out acid purification, then filter, and thick purification acid waste liquid is made.
In the step A1, the content of copper ion is 95g/L in acidic etching waste liquid, and the content of chlorion is 195g/L,
The content of organic additive is 0.7g/L, and the mass concentration of HCl is 4.4%；Organic additive determines agent, complexing agent and shield including ammonia
Bank agent, its weight ratio are 3:5:7；The dosage of sodium chlorate is 11g/L.
The step A2 is specially：It is 9.9 that the alkaline etching waste liquid for producing that content of copper ion is 115g/L is adjusted pH with ammonium hydroxide,
Coarse filtration is carried out, coarse filtration mesh number is 450 mesh, content of copper ion is reduced to 105g/L, and the filtrate after coarse filtration is added alkalescence purification
In tank, magnesium chloride is added, adjusting pH to 7.8 with ammonium hydroxide and polyacrylamide carries out alkaline purification, then filters, and is made thick net
Change alkaline waste liquor.
In the step A2, the content of copper ion is 115g/L in alkaline etching waste liquid for producing, and the content of chlorion is 190g/L；
The dosage of magnesium chloride is 11g/L.
The step B1 is specially：Thick purification alkalescence made from acid waste liquid and step A2 will be slightly purified made from step A1
Waste liquid is by weight 1.1:1 carries out neutralization reaction, obtains reaction solution, adjusts the pH to 6.7 of reaction solution, then carries out first time pressure
Filter, press filtration mesh number is 95 mesh, obtains first-time filtrate and a filter cake, and first-time filtrate is carried out smart filtering；
Wherein, the content of copper ion is 4.5g/L in first-time filtrate, and the content of chlorion is 88g/L；Copper in filter cake
The content of ion is 280kg/m3。
The step B2 is specially：The filter cake that step B1 is obtained adds water to be 1.6 by weight:Carried out after 1 mixing
Mashing, then carries out second of press filtration, obtains secondary filtrate and secondary filter cake；
Wherein, the content of copper ion is 0.4g/L in secondary filtrate, and the content of chlorion is 17g/L；Copper in secondary filter cake
The content of ion is 280kg/m3。
The step C1 is specially：The secondary filtrate that first-time filtrate after step B1 essence filterings and step B2 obtain is mixed
Close, obtain the mixing filtrate that content of copper ion is 6g/L, extracted with AB oil, obtain extract and waste liquid, extract is used
Sulfuric acid is stripped, and is repeatedly extracted and is stripped, and obtains the anti-stripping agent that content of copper ion is 44g/L；
The step D is specially：The secondary filter cake that the A liquid of the obtained copper ions of step C2 and the step B2 are obtained
It is beaten after mixing, adds the concentrated sulfuric acid that mass concentration is 98% and be acidified, then crystallize, feed is obtained after separation
Grade bluestone and mother liquor；
Alternatively, the step D is specially：The A liquid of the obtained copper ions of step C2, the step B2 are obtained secondary
It is beaten after the anti-stripping agent mixing that filter cake and the step C1 are obtained, adds the concentrated sulfuric acid that mass concentration is 98% and carry out
Acidifying, then crystallizes, feed-grade bluestone and mother liquor is obtained after separation.
Embodiment 5
The present embodiment and above-described embodiment 1 difference lies in：
The step A1 is specially：The acidic etching waste liquid that content of copper ion is 100g/L is subjected to coarse filtration, coarse filtration mesh number
For 500 mesh, content of copper ion is reduced to 80g/L, the filtrate after coarse filtration added in acid purification pot, adds sodium chlorate,
PH to 5.5 is adjusted with ammonium hydroxide and tap water and carries out acid purification, is then filtered, and thick purification acid waste liquid is made.
In the step A1, the content of copper ion is 100g/L in acidic etching waste liquid, and the content of chlorion is 200g/L,
The content of organic additive is 1.0g/L, and the mass concentration of HCl is 4.5%；Organic additive determines agent, complexing agent and shield including ammonia
Bank agent, its weight ratio are 4:6:8；The dosage of sodium chlorate is 12g/L.
The step A2 is specially：The alkaline etching waste liquid for producing that content of copper ion is 120g/L is adjusted pH with ammonium hydroxide is
10.0, coarse filtration is carried out, coarse filtration mesh number is 500 mesh, content of copper ion is reduced to 110g/L, and the filtrate after coarse filtration is added alkalescence
In purification pot, magnesium chloride is added, adjusting pH to 8 with ammonium hydroxide and polyacrylamide carries out alkaline purification, then filters, is made thick
Purify alkaline waste liquor.
In the step A2, the content of copper ion is 120g/L in alkaline etching waste liquid for producing, and the content of chlorion is 200g/L；
The dosage of magnesium chloride is 12g/L.
The step B1 is specially：Thick purification alkalescence made from acid waste liquid and step A2 will be slightly purified made from step A1
Waste liquid is by weight 1.2:1 carries out neutralization reaction, obtains reaction solution, adjusts the pH to 7 of reaction solution, then carries out first time pressure
Filter, press filtration mesh number is 100 mesh, obtains first-time filtrate and a filter cake, and first-time filtrate is carried out smart filtering；
Wherein, the content of copper ion is 5g/L in first-time filtrate, and the content of chlorion is 90g/L；In filter cake copper from
The content of son is 300kg/m3。
The step B2 is specially：The filter cake that step B1 is obtained adds water to be 1.7 by weight:Carried out after 1 mixing
Mashing, then carries out second of press filtration, obtains secondary filtrate and secondary filter cake；
Wherein, the content of copper ion is 0.5g/L in secondary filtrate, and the content of chlorion is 18g/L；Copper in secondary filter cake
The content of ion is 300kg/m3。
The step C1 is specially：The secondary filtrate that first-time filtrate after step B1 essence filterings and step B2 obtain is mixed
Close, obtain the mixing filtrate that content of copper ion is 7g/L, extracted with AB oil, obtain extract and waste liquid, extract is used
Sulfuric acid is stripped, and is repeatedly extracted and is stripped, and obtains the anti-stripping agent that content of copper ion is 45g/L；
The step D is specially：The secondary filter cake that the A liquid of the obtained copper ions of step C2 and the step B2 are obtained
It is beaten after mixing, adds the concentrated sulfuric acid that mass concentration is 99% and be acidified, then crystallize, feed is obtained after separation
Grade bluestone and mother liquor；
Alternatively, the step D is specially：The A liquid of the obtained copper ions of step C2, the step B2 are obtained secondary
It is beaten after the anti-stripping agent mixing that filter cake and the step C1 are obtained, adds the concentrated sulfuric acid that mass concentration is 99% and carry out
Acidifying, then crystallizes, feed-grade bluestone and mother liquor is obtained after separation.
The production technology of the present invention is become by the way that etching waste liquor waste utilization, the copper sulphate of generation, sub- liquid can be sold
Waste be changed into values, and the cost of etching waste liquor is 2000 yuan/ton, and the sub- liquid of recycling is 600-700 yuan/ton, the price of cupric sulfate purified
For 13000 yuan/ton or so, high financial profit.
The production process equipment of the present invention is simple, easy to operate, environment friendly and pollution-free, and no waste gas and wastes discharge, realizes waste
Utilize, mother liquid recycling, Zi Yehuishou enterprises, high financial profit.Copper ion in cupric sulfate purified produced by the present invention
Content is up to 98%, and production cost is low.
Above-described embodiment is the preferable implementation of the present invention, and in addition, the present invention can be realized with other manner,
Do not depart from and any on the premise of present inventive concept obviously replace within protection scope of the present invention.
Claims (7)
- A kind of 1. production technology of cupric sulfate purified, it is characterised in that：Include the following steps：A, the slightly preparation of purification etching waste liquor：The preparation of A1, thick purification acidic etching waste liquid：Cupric acidic etching waste liquid is subjected to coarse filtration, acid purification and filtering, system Obtain and slightly purify acid waste liquid；The preparation of A2, thick purification alkaline etching waste liquid for producing：Cupric alkaline etching waste liquid for producing is subjected to coarse filtration, alkalescence purification and filtering, system Obtain and slightly purify alkaline waste liquor；B, neutralization and press filtration：B1, will slightly purify thick purification alkaline waste liquor progress neutralization reaction made from acid waste liquid and step A2 made from step A1, Then first time press filtration is carried out, obtains first-time filtrate and a filter cake, and first-time filtrate is subjected to smart filtering；B2, a filter cake for obtaining step B1 add water to be beaten, and then carry out second of press filtration, obtain secondary filtrate and two Secondary filter cake；C, extraction and ion exchange：C1, extracted after the secondary filtrate that the first-time filtrate after step B1 essence filterings and step B2 obtain is mixed with AB oil, Extract and waste liquid are obtained, extract is stripped with sulfuric acid, obtains anti-stripping agent；Carry out first time ion exchange after C2, the waste liquid filtering for obtaining step C1, obtain copper ions A liquid and not cupric from The B liquid of son；C3, by the B liquid of the obtained not copper ions of step C2 add alkali to remove sulfate ion, then carries out the second secondary ion Exchange, to remove calcium ion, obtain the sub- liquid of not copper ions and calcium ion；D, acidifying and crystallization：It is beaten, is acidified after the secondary filter cake that the A liquid of the obtained copper ions of step C2 and the step B2 are obtained is mixed, Crystallization, obtains feed-grade bluestone and mother liquor；Alternatively, the obtained secondary filter cake of the A liquid of the obtained copper ions of step C2, the step B2 and the step C1 are obtained Anti-stripping agent mixing after be beaten, be acidified, crystallization, obtain feed-grade bluestone and mother liquor；E, purification and crystallization：The obtained feed-grade bluestones of step D are dissolved in water, carry out impurity and purification, then heating concentration, crystallization, is electroplated Grade bluestone；The step A1 is specially：The acidic etching waste liquid that content of copper ion is 80-100g/L is subjected to coarse filtration, coarse filtration mesh number is 300-500 mesh, makes content of copper ion be reduced to 70-80g/L, and the filtrate after coarse filtration is added in acid purification pot, adds chlorine Sour sodium, adjusts pH to 4.5-5.5 with ammonium hydroxide and tap water and carries out acid purification, then filter, thick purification acid waste liquid is made；Institute Stating step A2 is specially：It is 9.8-10.0 that the alkaline etching waste liquid for producing that content of copper ion is 100-120g/L is adjusted pH with ammonium hydroxide, Coarse filtration is carried out, coarse filtration mesh number is 300-500 mesh, content of copper ion is reduced to 90-110g/L, and the filtrate after coarse filtration is added alkali Property purification pot in, add magnesium chloride, adjusting pH to 7-8 with ammonium hydroxide and polyacrylamide carries out alkaline purification, then filters, system Obtain and slightly purify alkaline waste liquor.
- A kind of 2. cupric sulfate purified production technology according to claim 1, it is characterised in that：In the step A1, acid The content of copper ion is 80-100g/L in property etching waste liquor, and the content of chlorion is 180-200g/L, the content of organic additive For 0.1-1.0g/L, the mass concentration of HCl is 4.2-4.5%；Organic additive determines agent, complexing agent and shore protection agent including ammonia, its Weight ratio is 2-4:4-6:6-8；The dosage of sodium chlorate is 8-12g/L.
- A kind of 3. cupric sulfate purified production technology according to claim 1, it is characterised in that：In the step A2, alkali The content of copper ion is 100-120g/L in property etching waste liquor, and the content of chlorion is 160-200g/L；The dosage of magnesium chloride is 8-12g/L。
- A kind of 4. cupric sulfate purified production technology according to claim 1, it is characterised in that：The step B1 is specially：Thick purification alkaline waste liquor made from acid waste liquid and step A2 will be slightly purified made from step A1 By weight 0.8-1.2:1 carries out neutralization reaction, obtains reaction solution, adjusts the pH to 6-7 of reaction solution, then carries out first time pressure Filter, press filtration mesh number is 80-100 mesh, obtains first-time filtrate and a filter cake, and first-time filtrate is carried out smart filtering；Wherein, the content of copper ion is 3-5g/L in first-time filtrate, and the content of chlorion is 80-90g/L；In filter cake copper from The content of son is 250-300kg/m3。
- A kind of 5. cupric sulfate purified production technology according to claim 1, it is characterised in that：The step B2 is specially：The filter cake that step B1 is obtained adds water to be by weight 1.3-1.7:Carried out after 1 mixing Mashing, then carries out second of press filtration, obtains secondary filtrate and secondary filter cake；Wherein, the content of copper ion is 0.2-0.5g/L in secondary filtrate, and the content of chlorion is 14-18g/L；In secondary filter cake The content of copper ion is 250-300kg/m3。
- A kind of 6. cupric sulfate purified production technology according to claim 1, it is characterised in that：The step C1 is specially：The secondary filtrate that first-time filtrate after step B1 essence filterings and step B2 obtain is mixed, is obtained To the mixing filtrate that content of copper ion is 3-7g/L, extracted with AB oil, obtain extract and waste liquid, by extract sulfuric acid It is stripped, repeatedly extracts and be stripped, obtains the anti-stripping agent that content of copper ion is 40-45g/L；The step C2 is specially：After the waste liquid filtering that step C1 is obtained, add dilute sulfuric acid and carry out first time ion exchange, obtain To the A liquid of copper ions and the B liquid of non-copper ions；The step C3 is specially：The B liquid of the obtained not copper ions of step C2 is added into calcium hydroxide or calcium chloride to remove Sulfate ion, then carries out second of ion exchange, to remove calcium ion, obtains the sub- liquid of not copper ions and calcium ion.
- A kind of 7. cupric sulfate purified production technology according to claim 1, it is characterised in that：The step D is specially：The secondary filter cake that the A liquid of the obtained copper ions of step C2 and the step B2 are obtained mixes After be beaten, add mass concentration be 95-99% the concentrated sulfuric acid be acidified, then crystallize, electroplated after separation Grade bluestone and mother liquor；Alternatively, the step D is specially：The secondary filter cake that the A liquid of the obtained copper ions of step C2, the step B2 are obtained It is beaten after the anti-stripping agent mixing obtained with the step C1, adds the concentrated sulfuric acid that mass concentration is 95-99% and carry out Acidifying, then crystallizes, cupric sulfate purified and mother liquor is obtained after separation.
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| CN101717111A (en) * | 2008-10-09 | 2010-06-02 | 广州康瑞德生物技术股份有限公司 | Method for producing feed-grade bluestone by using cupreous etching waste liquor of circuit board |
| CN103693673A (en) * | 2013-12-25 | 2014-04-02 | 广州科城环保科技有限公司 | Producing method for producing electroplating grade copper sulfate with acid copper-bearing waste etching liquid |
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| CN101717111A (en) * | 2008-10-09 | 2010-06-02 | 广州康瑞德生物技术股份有限公司 | Method for producing feed-grade bluestone by using cupreous etching waste liquor of circuit board |
| CN103693673A (en) * | 2013-12-25 | 2014-04-02 | 广州科城环保科技有限公司 | Producing method for producing electroplating grade copper sulfate with acid copper-bearing waste etching liquid |
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| "利用含氯化铜蚀刻废液生产电镀级硫酸铜";深圳宇众环保科技有限公司;《亿商网》;20140424;第1页 * |
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| CF01 | Termination of patent right due to non-payment of annual fee |