CN108754158A - A kind of method of copper-contained sludge production cupric sulfate purified - Google Patents

A kind of method of copper-contained sludge production cupric sulfate purified Download PDF

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Publication number
CN108754158A
CN108754158A CN201810780164.9A CN201810780164A CN108754158A CN 108754158 A CN108754158 A CN 108754158A CN 201810780164 A CN201810780164 A CN 201810780164A CN 108754158 A CN108754158 A CN 108754158A
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copper
cupric sulfate
contained sludge
sulfate purified
filtrate
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Inventor
王伍
查正炯
吴阳东
王永成
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Guangzhou Kecheng Environmental Protection Technology Co Ltd
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Guangzhou Kecheng Environmental Protection Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/007—Wet processes by acid leaching
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0065—Leaching or slurrying
    • C22B15/0067—Leaching or slurrying with acids or salts thereof
    • C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0084—Treating solutions
    • C22B15/0086—Treating solutions by physical methods
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0084—Treating solutions
    • C22B15/0089—Treating solutions by chemical methods
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/30—Oximes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention discloses a kind of methods that copper-contained sludge produces cupric sulfate purified.The production method includes the following steps：It leaches：Copper-contained sludge is passed through into sulfuric acid leaching, is obtained by filtration and leaches filtrate；Removal of impurities：Lye is added in above-mentioned leaching filtrate, adjusts pH and removal of impurities filtrate is obtained by filtration；Extracting copper：Extractant extracting copper, the copper load organic phases after being extracted are added in above-mentioned removal of impurities filtrate；It is stripped copper：Copper-bath is obtained by extraction in copper load organic phases addition strippant；Condensing crystallizing：Cupric sulfate purified is prepared in copper-bath evaporation and concentration.The rate of recovery of the copper of this method reaches 96% or more, and product purity is high, technological process is simple, waste liquid in system can be recycled, generation waste liquid is few, and production cost is low, the recycling of copper suitable for high and low content copper-contained sludge, it is particularly suitable for handling the copper-contained sludge compared with low copper levels, effect is more economical.

Description

A kind of method of copper-contained sludge production cupric sulfate purified
Technical field
The present invention relates to chemical metallurgy technical fields, and in particular, to a kind of copper-contained sludge production cupric sulfate purified Method.
Background technology
Non-ferrous metal metallurgy, mechanical processing, electroplating industry will produce a large amount of copper-containing wastewaters, the prior art in process of production To the method that chemical precipitation is usually used in the processing of copper-containing wastewater, lime, liquid caustic soda etc. is added and forms copper-contained sludge.Copper-contained sludge In contain 1 ~ 10% copper, belong to hazardous waste, if dealing with improperly, copper in sludge can enter water body or soil, to pollute ring Border；In addition copper is as a kind of important non-renewable metal, and resource is more and more in short supply, and demand is higher and higher, therefore The copper in copper-contained sludge is recycled, the meaning of its recycling is very great.How effective Treatment of Copper sludge, and realize its nothing Evilization, recycling are always research emphasis both domestic and external.
Scientific research personnel mainly uses pyrometallurgical smelting recycling, acid adding leaching wet copper-contained sludge recycling treatment both at home and abroad at present Method recycling, calcining-acid adding leach three kinds of methods.Pyrometallurgical smelting recycling is to be dried in advance to copper-contained sludge, then uses lime As solvent, coke or high-temperature coal as fuel, high melt obtains blister copper for stone and fluorite.Pyrometallurgical smelting recovery method exists High energy consumption is unsuitable for handling low copper containing sludge to the disagreeableness disadvantage of environment, and to ingredient requirement height.Acid adding leaches wet method and returns It receives, this method copper recovery is low, process will produce toxic gas hydrogen sulfide.And so far there are no obtains electricity to copper-contained sludge recycling The report of plating copper sulphate.
Above-mentioned copper-contained sludge recoverying and utilizing method cannot all reach the recycling effect of environment-friendly high-efficiency, therefore provide a kind of The method that the low copper levels copper-contained sludge recycling of high-efficiency environment friendly prepares cupric sulfate purified has very important significance.
Invention content
The purpose of the present invention is intended to overcome the above-mentioned rate of recovery in the prior art low, and ingredient requirement is high and recovery method not ring The technical deficiencies such as guarantor provide a kind of method of copper-contained sludge production cupric sulfate purified.This method is suitable for different Cu content Copper-contained sludge, be particularly suitable for the copper-contained sludge of low copper levels, copper recovery is high, superior product quality.
The above-mentioned purpose of the present invention is achieved by following technical solution：
A kind of method of copper-contained sludge production cupric sulfate purified, includes the following steps：
S1. it leaches：Copper-contained sludge is leached by acid solution, Leaching Systems pH is 0.5 ~ 2.5, is obtained by filtration and leaches filtrate；
S2. it cleans：Lye is added in the leaching filtrate of above-mentioned S1, adjusts pH to 2.5 ~ 4.0, removal of impurities filtrate is obtained by filtration；
S3. extracting copper：Extractant extracting copper is added in removal of impurities filtrate in above-mentioned S2, the copper load after being extracted is organic Phase；
S4. it is stripped copper：Strippant is added in copper load organic phases in S3, copper-bath, the back extraction is obtained by extraction It is 0.5 ~ 2.0mol/L of sulfuric acid content, the solution of 0.3 ~ 1.0mol/L of content of copper ion to take agent；
S5. condensing crystallizing：Cupric sulfate purified is prepared in copper-bath evaporation and concentration in S4.
The leaching process preferably sulfuric acid of the present invention leaches copper-contained sludge, and control Leaching Systems pH's act as：It on the one hand can Utmostly to dissolve the copper ion leached in copper-contained sludge, the rate of recovery of copper in copper-contained sludge is improved, on the other hand can be reduced The addition of lye in follow-up removal step.
It is 2.5 ~ 4.0 to leaching filtrate systems to adjust pH again in dedoping step, it acts as：It on the one hand can be utmostly Precipitate and remove the impurity iron ion in solution, it is ensured that prepare the quality of cupric sulfate purified products material, on the other hand except While iron, iron hydroxide can be co-precipitated a large amount of impurity, such as metallic silicon, aluminium and some other organic impurities so that extract It not will produce interphase dirt in the process, avoid and cause the loss of extractant because interphase dirt is carried secretly, and accelerate two-phase point Layer is more advantageous to the progress of extraction reaction, improves the rate of recovery of copper.
In strip stage, as strippant, the hydrogen ion in sulfuric acid will be born for the mixed solution of sulfuric acid and copper sulphate The copper carried in organic phase replaces, and two hydrogen ions can replace a copper ion, by using containing specific molar concentration The solution of sulfuric acid and copper ion is stripped, and the advantage relative to conventional sulfuric acid extraction is：（1）It can will be stripped series It is reduced to 2-3 grades by conventional 5 ~ 6 grades；（2）The time that strip liquor reaches concentration needed for copper sulphate condensing crystallizing greatly shortens； （3）Reduce the generation of waste liquid during being stripped.
The recovery method technological process of the present invention is simple, at leaching, removal of impurities, organic extraction, copper-containing solution back extraction Reason so that the rate of recovery of copper reaches 96% or more, and the waste liquid in system can be recycled, and the organic phase of back extraction can be further It recycles and crystallizes the cupric sulphate crystal mother liquor of filtering in extraction step and can also further be recycled to be used in strip stage, The waste liquid of generation is few, and production cost is low, the recycling of copper suitable for the sludge of different Cu content, is particularly suitable for handling low copper and contains The sludge of amount, effect are more economical.
Wherein, above-mentioned lye can be the weak base of highly basic hydroxy, the weak base of carbonate or bicarbonate radical, it is preferable that Lye is sodium carbonate, sodium bicarbonate or sodium hydroxide solution.
Preferably, the volume ratio of strippant described in S4 and load organic phases is 2 ~ 8:1.
Preferably, copper load organic phases described in S4 passes through wash water carrying out washing treatment before back extraction, and the copper load is organic It is mutually 1 ~ 8 with the volume ratio of wash water:1.
Preferably, the wash water pH value is 0.5 ~ 4.
It is highly preferred that containing copper ion in the wash water, content of copper ion is 0.01 ~ 0.15mol/L.
Using acid wash water wash load organic phase, be conducive to be layered, split-phase is faster.It is molten using the acidity containing copper ion Liquid wash load organic phase, copper ion can displace the metal impurities being supported in organic phase so that the sulfuric acid being stripped Impurity iron ion content is lower in copper solution.The copper ion for adding certain content in acid wash water again, is replaced using copper ion The iron ion being supported in organic phase, and then be concentrated by evaporation and obtain the higher cupric sulfate pentahydrate product of quality, the waste water after washing It can also further be back in sludge beating process, non-wastewater discharge.
Preferably, sulfuric acid leaching operating procedure described in S1 is：By copper-contained sludge water with solid-to-liquid ratio 1:2 ~ 6 are beaten Processing, then 2 ~ 6h of Leach reaction, is obtained by filtration and leaches filtrate.
Copper-contained sludge filters 5 ~ 12% that remaining acid sludge is only copper-contained sludge volume itself after acidleach is handled, real The minimizing of sludge is showed, acid sludge can also be recycled further after washing, and water lotion can also return to sludge mashing In.The filter residue that removal of impurities processing is obtained by filtration can prepare ferric trichloride through persalt leaching, entire to leach dedoping step not Secondary pollution waste is will produce, waste water can recycle, environmental-friendly.
Preferably, extractant described in S3 is Mextral series extraction solution, and extractant and the volume ratio of removal of impurities filtrate are 1~5:1。
Preferably, the solution of Mextral series extractions described in S3 be volume ratio 5 ~ 40% Mextral extractants and 60 ~ 95% kerosene or the solution of 200# solvent naphthas.Mextral extractants be preferably Mextral84-I, Mextral973 or Mextral984。
Preferably, extraction time described in S3 is 1 ~ 20min.
Preferably, natural cooling crystallization described in S5 carries out under stiring, and mixing speed is 100 ~ 500r/min.Stirring speed Rate is excessive, and copper sulfate crystal nucleus can be caused to form time shortening, then cause product cut size smaller, powder is excessive.Stirring speed Rate is too small, copper sulfate crystal nucleus growth time lengthening, is easily mingled with impurity in crystal, and impurity content in product is caused to increase.
Preferably, it is concentrated by evaporation described in S5 to be concentrated by evaporation copper-bath in above-mentioned S4 to copper-bath Baume Degree is 42 ~ 52, stops heating natural cooling crystallization and obtains cupric sulphate crystal mother liquor, centrifugal filtration cupric sulphate crystal mother liquor obtains electricity Plate grade bluestone.
In order to promote effect of extracting, the extraction is single-stage or multitple extraction, and the back extraction is taken as single-stage or multistage back extraction It takes.
A kind of cupric sulfate purified produced by the above method.With the production method of the present invention from the cupric of different Cu content The purity of the sulfuric acid copper products produced in sludge can reach 98% or more, and iron ion content is less than 0.002%, zinc ion content Less than 0.001%, arsenic, cobalt, nickel, calcium ion content be below 0.0005%, cupric sulfate purified high-class product can be fully met （HG/T 3592-2010）Quality requirements.
Compared with prior art, the present invention has the advantages that：
The present invention provides a kind of methods that copper-contained sludge produces cupric sulfate purified, utilize sulfuric acid leaching, removal of impurities processing and sulphur Sour copper solution back extraction produces cupric sulfate purified from copper-contained sludge, and the rate of recovery of copper reaches 96% or more, and product purity Height, technological process is simple, and the waste liquid in the preparation system of method of the invention can be recycled, and generation waste liquid is few, production cost Low, the recycling of copper suitable for high low content copper sludge is particularly suitable for processing low content copper sludge, and effect is more economical.
Specific implementation mode
The present invention is further illustrated With reference to embodiment, but embodiment the present invention is not done it is any The restriction of form.Unless otherwise indicated, source chemicals used in the embodiment of the present invention are the source chemicals routinely bought.
Copper-contained sludge material composition used in the embodiment of the present invention see the table below 1.
Table 1
Ingredient Copper Arsenic Lead Calcium Iron Cobalt Nickel Zinc
Content/% 1-4 < 0.01 < 0.01 < 0.1 < 8 < 0.01 < 0.1 < 0.1
Cupric sulfate purified（HG/T 3592-2010）Product main standard is as shown in table 2.
Table 2
Ingredient Copper Arsenic Lead Calcium Iron Cobalt Nickel Zinc
High-class product/% ≥98 ≤0.0005 ≤0.001 ≤0.0005 ≤0.002 ≤0.0005 ≤0.0005 ≤0.001
Embodiment 1 ~ 10
A kind of method of copper-contained sludge production cupric sulfate purified, includes the following steps：
S1. it leaches：Copper-contained sludge is passed through into sulfuric acid leaching, controls Leaching Systems pH, is obtained by filtration and leaches filtrate；
S2. it cleans：Lye is added in the leaching filtrate of above-mentioned S1, adjusts pH, removal of impurities filtrate is obtained by filtration；
S3. extracting copper：Mextral series extraction agent extracting coppers are added in removal of impurities filtrate in above-mentioned S2, after being extracted Copper load organic phases, extractant are 3 with filtering and impurity removing liquid volume ratio:1, extraction time 10min；
S4. it is stripped copper：Strippant is added in copper load organic phases in S3, copper-bath is obtained by extraction；
S5. condensing crystallizing：Cupric sulfate purified is prepared in copper-bath evaporation and concentration in S4, water phase copper sulphate is molten Liquid is concentrated by evaporation, and when copper-bath Baume degrees is 45, is stopped heating natural cooling crystallization and is obtained cupric sulphate crystal mother liquor, from Heart filtering cupric sulphate crystal mother liquor obtains cupric sulfate pentahydrate.
Extractant is 5%Mextral84-I and 95% kerosene wherein in embodiment 1.
Extractant is 40%Mextral973 and 60%200# solvent naphthas in embodiment 2.
Extractant is 20%Mextral984 and 80%200# solvent naphthas in embodiment 3.
Other embodiment and extractant in embodiment 1 and identical with aqueous slkali.Specific parameter such as table 3 in each embodiment It is shown：
Wherein A is Leaching Systems pH value in S1, and B is removal of impurities system pH, and C is the volume ratio of strippant and load organic phases, D For sulfuric acid content mol/L in strippant, content of copper ion E mol/L in strippant.
Table 3
Serial number A B C D E
Embodiment 1 1.5 2.5 5:1 1 0.5
Embodiment 2 0.5 3 5:1 1 0.5
Embodiment 3 2.5 3 5:1 1 0.5
Embodiment 4 1.5 4 5:1 1 0.5
Embodiment 5 1.5 3 2:1 1 0.5
Embodiment 6 1.5 3 8:1 1 0.5
Embodiment 7 1.5 3 5:1 0.5 0.5
Embodiment 8 1.5 3 5:1 2 0.5
Embodiment 9 1.5 3 5:1 1 0.3
Embodiment 10 1.5 3 5:1 1 1
Embodiment 11
A kind of method of copper-contained sludge production cupric sulfate purified, substantially the same manner as Example 1, difference lies in copper is negative in S4 It carries organic phase and passes through wash water carrying out washing treatment before back extraction, the volume ratio of copper load organic phases and wash water is 4:1, wash water pH value is 2。
Embodiment 12
A kind of method of copper-contained sludge production cupric sulfate purified, substantially the same manner as Example 1, difference lies in copper is negative in S4 It carries organic phase and passes through wash water carrying out washing treatment before back extraction, the volume ratio of copper load organic phases and wash water is 1:1, wash water pH value is 2。
Embodiment 13
A kind of method of copper-contained sludge production cupric sulfate purified, substantially the same manner as Example 1, difference lies in copper is negative in S4 It carries organic phase and passes through wash water carrying out washing treatment before back extraction, the volume ratio of copper load organic phases and wash water is 8:1, wash water is pH value It is 2.
Embodiment 14
A kind of method of copper-contained sludge production cupric sulfate purified, substantially the same manner as Example 1, difference lies in copper is negative in S4 It carries organic phase and passes through wash water carrying out washing treatment before back extraction, the volume ratio of copper load organic phases and wash water is 4:1, wash water is pH value It is 0.5.
Embodiment 15
A kind of method of copper-contained sludge production cupric sulfate purified, substantially the same manner as Example 1, difference lies in copper is negative in S4 It carries organic phase and passes through wash water carrying out washing treatment before back extraction, the volume ratio of copper load organic phases and wash water is 4:1, wash water is pH value It is 4.
Embodiment 16
A kind of method of copper-contained sludge production cupric sulfate purified, substantially the same manner as Example 1, difference lies in copper is negative in S4 It carries organic phase and passes through wash water carrying out washing treatment before back extraction, the volume ratio of copper load organic phases and wash water is 4:1, wash water is pH value It is 2, copper ion, content of copper ion 0.1mol/L is contained in wash water.
Embodiment 17
A kind of method of copper-contained sludge production cupric sulfate purified, substantially the same manner as Example 1, difference lies in copper is negative in S4 It carries organic phase and passes through wash water carrying out washing treatment before back extraction, the volume ratio of copper load organic phases and wash water is 4:1, wash water is pH value It is 2, copper ion, content of copper ion 0.01mol/L is contained in wash water.
Embodiment 18
A kind of method of copper-contained sludge production cupric sulfate purified, substantially the same manner as Example 1, difference lies in the leachings in S1 Go out for by copper-contained sludge water with solid-to-liquid ratio 1:4 carry out mashing processing, and then the addition concentrated sulfuric acid to system pH is 2, Leach reaction 4h is obtained by filtration and leaches filtrate.
Embodiment 19
A kind of method of copper-contained sludge production cupric sulfate purified, it is substantially the same manner as Example 1, difference lies in,
Leaching in S1 is by copper-contained sludge water with solid-to-liquid ratio 1:4 carry out mashing processing, and the concentrated sulfuric acid is then added to system pH It is 2, Leach reaction 4h is obtained by filtration and leaches filtrate；Copper load organic phases pass through wash water carrying out washing treatment, copper before back extraction in S4 Load organic phases and the volume ratio of wash water are 4:1, wash water pH value is 2, contains copper ion, content of copper ion 0. in wash water 1mol/L。
Comparative example 1 ~ 8
The step of comparative example 1 ~ 8, is substantially the same manner as Example 1, and specific parameter of distinguishing is shown in Table 4.
Table 4
Serial number A B C D
Comparative example 1 3 3 5:1 1
Comparative example 2 0.25 3 5:1 1
Comparative example 3 1.5 2 5:1 1
Comparative example 4 1.5 5 5:1 1
Comparative example 5 1.5 3 1:1 1
Comparative example 6 1.5 3 9:1 1
Comparative example 7 1.5 3 5:1 0.3
Comparative example 8 1.5 3 5:1 2.1
Evaluation of result
The purity of copper sulphate in embodiment and comparative example, the detection method foundation of impurity iron content《Plating copper sulphate》（HG/ T3592-2010）.Testing result is shown in Table 5.
The computational methods of the rate of recovery of copper are in copper-contained sludge：The rate of recovery of copper=（Quality-raffinate copper of removal of impurities liquid copper Quality）Quality × 100% of copper in/copper-contained sludge.
Table 5
Serial number Purity/% of copper sulphate Iron content/% The rate of recovery/% of copper
Embodiment 1 98.67 0.0016 96.48
Embodiment 2 98.98 0.0008 98.15
Embodiment 3 98.58 0.0009 96.11
Embodiment 4 99.01 0.0003 96.77
Embodiment 5 98.48 0.0008 97.55
Embodiment 6 99.09 0.0007 97.19
Embodiment 7 98.10 0.0014 97.25
Embodiment 8 98.58 0.0008 96.68
Embodiment 9 98.96 0.0012 96.78
Embodiment 10 98.69 0.0007 96.56
Embodiment 11 98.97 0.0008 96.53
Embodiment 12 99.12 0.0005 96.85
Embodiment 13 98.76 0.0012 97.10
Embodiment 14 98.86 0.0006 96.94
Embodiment 15 98.95 0.0010 96.67
Embodiment 16 99.35 0.0004 96.78
Embodiment 17 99.21 0.0005 96.61
Embodiment 18 99.05 0.0010 97.59
Embodiment 19 99.25 0.0009 97.41
Comparative example 1 97.22 0.0018 56.56
Comparative example 2 98.55 0.0014 90.11
Comparative example 3 98.11 0.0048 90.41
Comparative example 4 97.78 0.0009 75.88
Comparative example 5 95.26 0.0028 91.86
Comparative example 6 95.88 0.0035 91.35
Comparative example 7 94.31 0.0024 90.26
Comparative example 8 98.52 0.0023 90.18
It can be seen that the purity of the copper sulphate of the sludge remanufacture in embodiment using different Cu content from above-mentioned testing result 98% or more can be reached, the content of impurity iron is all 0.002% hereinafter, the rate of recovery of copper exists in sludge in sulfuric acid copper products 96% or more, meet the standard for closing cupric sulfate purified, the good product quality of production, copper recovery height.Relative to comparison number of cases According to the purity of copper sulphate prepared by remanufacture method of the invention is apparently higher than comparative example, illustrates the remanufacture of the present invention Method can preferably recycle the copper resource in copper-contained sludge, and it is dirty to be more suitable for various various concentrations, especially low concentration cupric The resource utilization of mud utilizes.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair The restriction of embodiments of the present invention.For those of ordinary skill in the art, may be used also on the basis of the above description To make other variations or changes in different ways.There is no necessity and possibility to exhaust all the enbodiments.It is all this All any modification, equivalent and improvement etc., should be included in the claims in the present invention made by within the spirit and principle of invention Protection domain within.

Claims (15)

1. a kind of method of copper-contained sludge production cupric sulfate purified, which is characterized in that include the following steps：
S1. it leaches：Copper-contained sludge is leached through acid solution, Leaching Systems pH is 0.5 ~ 2.5, is obtained by filtration and leaches filtrate；
S2. it cleans：Lye is added in the leaching filtrate of above-mentioned S1, adjusts pH to 2.5 ~ 4.0, removal of impurities filtrate is obtained by filtration；
S3. extracting copper：Extractant extracting copper is added in removal of impurities filtrate in above-mentioned S2, the copper load after being extracted is organic Phase；
S4. it is stripped copper：Strippant is added in copper load organic phases in S3, copper-bath, the back extraction is obtained by extraction It is 0.5 ~ 2.0mol/L of sulfuric acid content, the solution of 0.3 ~ 1.0mol/L of content of copper ion to take agent；
S5. concentrated acid crystallizes：Cupric sulfate purified is prepared in copper-bath evaporation and concentration in S4.
2. the method for copper-contained sludge production cupric sulfate purified as described in claim 1, which is characterized in that be stripped described in S4 The volume ratio of agent and load organic phases is 2 ~ 8:1.
3. the method for copper-contained sludge production cupric sulfate purified as described in claim 1, which is characterized in that copper described in S4 loads Organic phase passes through wash water carrying out washing treatment before back extraction, and the volume ratio of the copper load organic phases and wash water is 1 ~ 8:1.
4. the method for copper-contained sludge production cupric sulfate purified as claimed in claim 3, which is characterized in that the wash water is pH value It is 0.5 ~ 4.
5. the method for copper-contained sludge production cupric sulfate purified as claimed in claim 4, which is characterized in that contain in the wash water Copper ion, content of copper ion are 0.01 ~ 0.15mol/L.
6. the method for copper-contained sludge production cupric sulfate purified as described in claim 1, which is characterized in that leach behaviour described in S1 It is as step：By copper-contained sludge water with solid-to-liquid ratio for 1:2 ~ 6 carry out mashing processing, and then 2 ~ 6h of Leach reaction, is obtained by filtration Leach filtrate.
7. the method for copper-contained sludge production cupric sulfate purified as described in claim 1, which is characterized in that extractant described in S3 For Mextral series extraction solution, the volume ratio of extractant and removal of impurities filtrate is 1 ~ 5:1.
8. the method for copper-contained sludge as claimed in claim 7 production cupric sulfate purified, which is characterized in that the extraction time is 1~20min。
9. the method for copper-contained sludge production cupric sulfate purified as described in claim 1, which is characterized in that naturally cold described in S5 But it crystallizes and carries out under stiring, mixing speed is 100 ~ 500r/min.
10. a kind of cupric sulfate purified by the method production of any one of the claims 1 ~ 9.
CN201810780164.9A 2018-07-16 2018-07-16 A kind of method of copper-contained sludge production cupric sulfate purified Pending CN108754158A (en)

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CN113443774A (en) * 2021-07-23 2021-09-28 深圳市环保科技集团有限公司 Treatment method and treatment system for copper-iron-containing wastewater

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110184459A (en) * 2019-05-10 2019-08-30 广州科城环保科技有限公司 A method of basic copper chloride is produced using copper-contained sludge
CN113443774A (en) * 2021-07-23 2021-09-28 深圳市环保科技集团有限公司 Treatment method and treatment system for copper-iron-containing wastewater

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