CN106495205B - A kind of cupric sulfate purified and its production technology - Google Patents

A kind of cupric sulfate purified and its production technology Download PDF

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Publication number
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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content
liquid
purification
ion
filtrate
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CN106495205A (en
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邱国华
罗海平
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Dongguan Derui Industrial Waste Treatment Co ltd
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Dongguan Xinyi Industrial Waste Treatment Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00Compounds of copper
    • C01G3/10Sulfates
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00Compounds of copper
    • C01G3/003Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/80Compositional purity

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  • Inorganic Chemistry (AREA)
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  • 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

A kind of cupric sulfate purified and its production technology
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)

  1. 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.
  2. 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.
  3. 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。
  4. 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
  5. 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
  6. 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.
  7. 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.
CN201611016408.3A 2016-11-18 2016-11-18 A kind of cupric sulfate purified and its production technology Expired - Fee Related CN106495205B (en)

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CN110156233A (en) * 2019-06-11 2019-08-23 无锡威孚环保催化剂有限公司 A method of processing Cu-SSZ-13 molecular sieve waste liquid

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