CN110158089A - The alkalinity erosion copper waste liquor recovery process method of zero-emission - Google Patents
The alkalinity erosion copper waste liquor recovery process method of zero-emission Download PDFInfo
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- 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
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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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
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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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/46—Regeneration of etching compositions
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- 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
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Abstract
The present invention discloses a kind of alkalinity erosion copper waste liquor recovery process method of zero-emission, comprising the following steps: hydrochloric acid is added in the erosion copper waste liquid flowed out to etching machine, the hydrochloric acid makes to lose the copper ammonia complexation ion contact break precipitating in copper waste liquid；The erosion copper waste liquid of contact break precipitating is sent into equipment for separating liquid from solid, clear liquid and copper sludge are isolated by the equipment for separating liquid from solid；Ammonia auxiliary agent is added into the clear liquid, the clear liquid is by being added the Ammonia auxiliary agent formation alkaline etch bath and adding in the etching machine；Concentrated sulfuric acid dissolution is added after mashing in the copper sludge, prepares copper sulphate mixed liquor, crystallisation by cooling, dehydration separate up to technical grade sulfuric acid copper the copper sulphate mixed liquor again.The present invention has been truly realized zero-emission, thoroughly solves problem of environmental pollution caused by erosion copper waste liquid.Also, this process is simple, and treatment effeciency is high, and low energy consumption, and required equipment is few, greatly reduces cost recovery.
Description
Technical field
The present invention relates to erosion copper devil liquor recovery technical field, in particular to the alkalinity erosion copper devil liquor recovery works of a kind of zero-emission
Process.
Background technique
Alkaline etching liquid is generally produced by professional electronics chemical plant, fresh alkaline etching liquid, general also known as son
Liquid, main component are ammonium chloride [NH4Cl] and ammonium hydroxide [NH3·H2O].Alkaline etching liquid is added in etching machine and copper etching liquor
[CuCl2] reaction form copper ammonia complexation ion [Cu (NH3)4]2+, [Cu (NH3)4]2+It, can be with copper foil with very strong oxidisability
Redox reaction occurs, so that copper foil be dissolved.Cu during redox reaction, in copper etching liquor2+Ion concentration
Can be higher and higher, work as Cu2+Ion concentration is close to when being saturated, and etching speed instead can be slack-off, general control Cu2+The concentration of ion
It for 140~150g/L, is automatically adjusted thus by densimeter, continuous exclusive segment dope, and fresh alkalinity erosion is added in equivalent
Liquid is carved, and the part dope being discharged is to lose copper waste liquid.
Lose copper waste liquid mainly by [Cu (NH3)4]2+、NH4Cl、H2O and trace mineral supplement composition, wherein Cu2+Ion it is dense
Degree is 12.0%, Cl-The concentration of ion is 16.5%, NH4 +The concentration of ion is 8.5%.Lose the Cu in copper waste liquid2+Ion is attached most importance to
Metal ion, if be arbitrarily discharged into water body, especially Drinking w ater will lead to human poisoning, harmful human health；
NH4 +Ion is the eutrophy ingredient of microorganism and algae, promotes the flourish of microorganism and algae, while needing a large amount of absorb
Dissolved oxygen in water leads to water body severe depletion of oxygen, causes the death of aquatic animal (fishes and shrimps etc.) and its hair that rots is smelt, destroy ecology
Environment jeopardizes human health.Therefore, the part erosion copper waste liquid of environmental protection administration's discharge is referred to as " hazardous waste ", and national regulation is wanted
It is handled by Tong Shouhou specialized department, environmental protection administration.
Environmentally friendly state basic policy according to " being administered from root, comprehensively utilize ".Copper etching liquor reaches quilt after saturation due to constantly losing copper
Discharge becomes " hazardous waste ", during entirely erosion copper, NH4The amount of Cl does not change always.We gain enlightenment from here,
As long as the copper lost in copper waste liquid is taken out and reusable.How copper is taken out? present society it is relatively common be " extraction
Take electrolysis method ".Method particularly includes: firstly, organic extractant is added in erosion copper waste liquid, form organic copper complexing not soluble in water
Object, then static layering, lower layer are that aqueous solution returns to etching machine as sub- liquid, and upper layer is that organic copper complex is sent to next process；
Then, enriching sulfuric acid contact break, the organic copper complex separated generate complexing agent [RH in conjunction with hydrogen ion in sulfuric acid2] return
Extraction process, sulfate radical [SO4 2-] and [Cu2+] generate copper-bath；Finally, electrolysis copper sulphate, copper sulphate are sent to electrolyzer electric
Solution obtains copper pool and the useless dilution heat of sulfuric acid containing a small amount of copper sulphate.There are following defects for this method:
(1) not only trouble is added to environmental protection instead: when concentrated sulfuric acid contact break, regenerating etching solution without solving environmental issue
Zigzag is become to lines lateral erosion containing a small amount of ammonium sulfate, can be broken when serious, circulation a period of time must discharge, and institute is not in order to avoid
The discharge of " hazardous waste "；Also, solution fever generates the exhaust gas such as a large amount of water vapours, ammonia and acid gas, seriously pollutes environment,
Waste gas absorbing system equipment must be increased and reduce environmental pollution；In addition, concentrated sulfuric acid contact break, is consumed dense every year with daily 1 ton of copper
120 tons of sulfuric acid calculating, become dilute sulfuric acid and at least form 300 tons of useless dilute sulfuric acids, undoubtedly increase the discharge of useless dilute sulfuric acid after electrolysis.
(2) processing method is long, equipment investment is big: pressing 10m3/ d estimation, complete equipment (extraction, separation, contact break, electricity
Solution, exhaust gas are inhaled etc.) minimum 3,000,000 yuan of input cost；
(3) it is at high cost to mention copper: extracting minimum 12000 yuan of input cost of 1 ton of copper cost.
Above content is only used for the technical solution that auxiliary understands the application, does not represent and recognizes that above content is existing skill
Art.
Summary of the invention
The main object of the present invention is to provide a kind of alkalinity erosion copper waste liquor recovery process method of zero-emission, it is intended to solve existing
Have that environmental pollution present in recovery process is big, recovery process is long, equipment investment is big, proposes the problems such as copper is at high cost.
To achieve the above object, the present invention proposes a kind of alkalinity erosion copper waste liquor recovery process method of zero-emission, including with
Lower step:
Hydrochloric acid is added in the erosion copper waste liquid flowed out to etching machine in S1, the hydrochloric acid make to lose the copper ammonia complexation in copper waste liquid from
Sub- contact break precipitating；
The erosion copper waste liquid of contact break precipitating is sent into equipment for separating liquid from solid, is separated by the equipment for separating liquid from solid by S2
Clear liquid and copper sludge out；
Ammonia auxiliary agent is added in S3, Xiang Suoshu clear liquid, the clear liquid forms alkaline etch by the way that the Ammonia auxiliary agent is added
Liquid simultaneously adds in the etching machine；
S4, the copper sludge are added concentrated sulfuric acid dissolution after mashing, prepare copper sulphate mixed liquor, the copper sulphate mixed liquor
Crystallisation by cooling again, dehydration separate up to technical grade sulfuric acid copper.
Optionally, the hydrochloric acid is added in S1 step in the alkalinity erosion copper waste liquor recovery process method of the zero-emission
The pH value for adjusting erosion copper waste liquid is 3.5~6.5, makes to lose the copper ammonia complexation ion contact break precipitating in copper waste liquid.
Optionally, the alkalinity erosion copper waste liquor recovery process method of the zero-emission, in S2 step, the separation of solid and liquid
Device is filter press, and the erosion copper waste liquid of contact break precipitating is pumped into the filter press, isolates clear liquid by the filter press
And copper sludge.
Optionally, the alkalinity erosion copper waste liquor recovery process method of the zero-emission, in the S3 step, the Ammonia auxiliary agent
For one or both of ammonium hydroxide and ammonia, it is 9.5~11.5 that the Ammonia auxiliary agent, which is added, and adjusts the pH value of the clear liquid.
Optionally, the alkalinity erosion copper waste liquor recovery process method of the zero-emission detects the clear liquid in the S3 step
The concentration of middle chloride ion, the clear liquid forms alkaline etch bath after the Concentration Testing of the chloride ion is qualified.
Optionally, the alkalinity erosion copper waste liquor recovery process method of the zero-emission, in S4 step, in Xiang Suoshu copper sludge
The concentration that copper sulphate mother liquor is added to be beaten, and controls the copper sludge is 40Be`~50Be`.
Optionally, the alkalinity erosion copper waste liquor recovery process method of the zero-emission, when the copper sulphate mother liquor deficiency,
Concentration by the way that copper sludge described in water management is added is 40Be`~50Be`.
Optionally, the alkalinity erosion copper waste liquor recovery process method of the zero-emission is added while stirring in S4 step
The concentrated sulfuric acid stops the addition of the concentrated sulfuric acid when concentration for the concentrated sulfuric acid that dissociates is 10g/L.
Optionally, the alkalinity erosion copper waste liquor recovery process method of the zero-emission, in S4 step, the copper sulphate is mixed
It closes liquid and is cooled to 30 DEG C~35 DEG C in 3 hours, copper sulphate completes crystallization in the copper sulphate mixed liquor.
Optionally, the alkalinity erosion copper waste liquor recovery process method of the zero-emission, in S4 step, the crystallisation by cooling
Copper sulphate mixed liquor dehydration separation is carried out using centrifuge, the upper layer copper sulphate mother liquor after separation is for being beaten.
Technical solution of the present invention is precipitated by using the copper ammonia complexation ion contact break that hydrochloric acid makes to lose in copper waste liquid, is isolated clear
Ammonia auxiliary agent is added in clear liquid and forms alkaline etch bath and adds to the etching machine for liquid and copper sludge, and acid adding is molten after copper sludge mashing
Solution, crystallisation by cooling isolate technical grade sulfuric acid copper.The present invention has been truly realized zero-emission, thoroughly solves caused by erosion copper waste liquid
Problem of environmental pollution.Also, this process is simple, and treatment effeciency is high, and low energy consumption, and required equipment is few, greatly reduces back
Harvest sheet.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
Other relevant attached drawings are obtained according to these attached drawings.
Fig. 1 is the process signal of an embodiment of the alkalinity erosion copper waste liquor recovery process method of zero-emission provided by the invention
Figure.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
The present invention proposes a kind of alkalinity erosion copper waste liquor recovery process method of zero-emission, for solving caused by erosion copper waste liquid
Problem of environmental pollution.
Referring to Fig.1, Fig. 1 is an embodiment of the alkalinity erosion copper waste liquor recovery process method of zero-emission provided by the invention
Flow diagram.
In embodiments of the present invention, a kind of alkalinity erosion copper waste liquor recovery process method of zero-emission, comprising the following steps:
Hydrochloric acid is added in the erosion copper waste liquid flowed out to etching machine in S1, the hydrochloric acid make to lose the copper ammonia complexation in copper waste liquid from
Sub- contact break precipitating；
The erosion copper waste liquid of contact break precipitating is sent into equipment for separating liquid from solid, is separated by the equipment for separating liquid from solid by S2
Clear liquid and copper sludge out；
Ammonia auxiliary agent is added in S3, Xiang Suoshu clear liquid, the clear liquid forms alkaline etch by the way that the Ammonia auxiliary agent is added
Liquid simultaneously adds in the etching machine；
S4, the copper sludge are added concentrated sulfuric acid dissolution after mashing, prepare copper sulphate mixed liquor, the copper sulphate mixed liquor
Crystallisation by cooling again, dehydration separate up to technical grade sulfuric acid copper.
Copper in erosion copper waste liquid is lost in copper waste liquid existing for copper ammonia complexation ionic species when hydrochloric acid is added to
Afterwards, hydrochloric acid and copper ammonia complexation ionic reaction generate basic copper chloride Cu2Cl(OH)3Precipitating or Kocide SD Cu (OH)2Precipitating,
To achieve the effect that copper ammonia complexation ion contact break precipitates, reaction principle is as follows:
2[Cu(NH3)4]2++Cl-+5H++3H2O→Cu2Cl(OH)3↓+8NH4 +；
[Cu(NH3)4]2++2H++2H2O→Cu(OH)2↓+4NH4 +；
Technical solution of the present invention is precipitated by using the copper ammonia complexation ion contact break that hydrochloric acid makes to lose in copper waste liquid, is isolated clear
Ammonia auxiliary agent is added in clear liquid and forms alkaline etch bath and adds to the etching machine for liquid and copper sludge, and acid adding is molten after copper sludge mashing
Solution, crystallisation by cooling isolate technical grade sulfuric acid copper.The present invention has been truly realized zero-emission, thoroughly solves caused by erosion copper waste liquid
Problem of environmental pollution.
Optionally, in S1 step, it is 3.5~6.5 that the hydrochloric acid, which is added, and adjusts the pH value of erosion copper waste liquid, makes to lose copper waste liquid
In copper ammonia complexation ion contact break precipitating.When the pH value for losing copper waste liquid is lower than 3.5, precipitated copper sludge can be re-dissolved,
The rate of recovery of copper is reduced, discharge be easy to cause heavy metal pollution；And when the pH value for losing copper waste liquid is higher than 6.5, take off network
Power is inadequate, and copper ammonia complexation ion cannot be precipitated completely, not can guarantee copper and be essentially completely recovered, and equally will also result in environment dirt
Dye.
Optionally, in S2 step, the equipment for separating liquid from solid includes filter press, the erosion copper waste drains pump of contact break precipitating
Enter to the filter press, clear liquid and copper sludge are isolated by the filter press.It is of course also possible to use other separation of solid and liquid sides
Formula, including gravity filtration, pressure filtration and vacuum filter etc. realize that the mode of separation of solid and liquid has very much, herein just not one by one
It repeats.
Optionally, in the S3 step, the Ammonia auxiliary agent is one or both of ammonium hydroxide and ammonia, and the Ammonia is added
The pH value that auxiliary agent adjusts the clear liquid is 9.5~11.5.The embodiment of the present invention is by being added the hydrogen in Ammonia auxiliary agent and in clear liquid
Ion, the pH value for adjusting the clear liquid is 9.5~11.5, controls the ratio of ammonium chloride and ammonium hydroxide in clear liquid, ensure that cuprammonium
Complex ion quickly generates.
Preferably, in the S3 step, the concentration for detecting chloride ion in the clear liquid, when the Concentration Testing of the chloride ion closes
The clear liquid forms alkaline etch bath after lattice.The clear liquid forms alkaline etch bath after chloride ion content is qualified in the clear liquid
It can add in the etching machine, this ensure that clear liquid is consistent with the ingredient of alkaline etch bath, cyclically use clear liquid, no
Environmental pollution caused by being expelled directly out clear liquid is only avoided, and reduces the cost recovery of erosion copper waste liquid, avoids reagent
Waste.
Optionally, copper sulphate mother liquor is added in S4 step, in Xiang Suoshu copper sludge to be beaten, and controls the copper sludge
Concentration is 40~50Be`.The present invention is by mashing so that copper sludge is sufficiently swollen in copper sulphate mother liquor, to add sulfuric acid molten in next step
Solution is ready.Also, the present invention makes full use of copper sulphate mother liquor to be beaten, and on the one hand avoids the waste of copper sulphate mother liquor, separately
On the one hand, it ensure that the copper in copper sulphate mother liquor is fully extracted, improve the rate of recovery of copper.It will be apparent that copper sludge
Concentration can neither it is too high can not be too low, otherwise not can guarantee copper sludge and be sufficiently swollen.
Optionally, when the copper sulphate mother liquor deficiency, the concentration by the way that copper sludge described in water management is added is 40~50Be
`.In order to guarantee that copper sludge is sufficiently swollen, when copper sulphate mother liquor deficiency, the present invention controls the copper by adding water to supply solvent
The concentration of mud is 40~50Be`.
Optionally, in S4 step, the concentrated sulfuric acid is added while stirring, until the concentration for the concentrated sulfuric acid that dissociates is 10g/L
When, stop the addition of the concentrated sulfuric acid.In embodiments of the present invention, the concentrated sulfuric acid is added while stirring, so that the concentrated sulfuric acid is mixed with copper sludge
Uniformly, it ensure that copper sludge dissolution reaction thoroughly carries out.When the concentration of the free concentrated sulfuric acid is 10g/L, stop the addition of the concentrated sulfuric acid,
Copper sludge is completely dissolved at this time, avoids the waste of the concentrated sulfuric acid.
Optionally, in S4 step, the copper sulphate mixed liquor is cooled to 30 DEG C~35 DEG C in 3 hours, the sulfuric acid
Copper sulphate completes crystallization in copper mixed liquor.The present invention ensure that copper sulphate is tied completely by control cooling velocity and cooling temperature
Crystalline substance, further such that the copper in erosion copper waste liquid is sufficiently recycled.
Optionally, in S4 step, the copper sulphate mixed liquor of the crystallisation by cooling carries out dehydration separation using centrifuge, point
Upper layer copper sulphate mother liquor from after is for being beaten.The present invention is by the isolated upper layer copper sulphate mother liquor of centrifuge, and by upper layer
The mashing of copper sulphate mother liquor, on the one hand avoids the waste of reagent, mitigates discharging of waste liquid, on the other hand ensure that in copper sulphate mother liquor
Copper be fully extracted.
In addition, the heretofore described concentrated sulfuric acid is the sulfuric acid that mass fraction is 98%.
Technical solution of the present invention is described in further detail below in conjunction with specific embodiment, it should be understood that following real
It applies example to be only used to explain the present invention, be not intended to limit the present invention.
Embodiment 1
(1) contact break precipitates
Hydrochloric acid is added while stirring in the erosion copper waste liquid flowed out to etching machine, is by the pH value that hydrochloric acid adjusts erosion copper waste liquid
3.5~6.5, so that the copper ammonia complexation ion contact break precipitating in erosion copper waste liquid；
(2) it is separated by solid-liquid separation
The erosion copper waste liquid that contact break precipitates is pumped into filter press, the pump pressure of filter press is 4.0kg/cm2, by described
Equipment for separating liquid from solid isolates clear liquid and copper sludge, and the clear liquid is NH4Cl solution, the copper content of the copper sludge are 35% or so；
(3) clear liquid recycles
Chloride ion content in the clear liquid is detected, ammonium hydroxide is added in Xiang Suoshu clear liquid, clear liquid is adjusted by the ammonium hydroxide
PH value is 3.5~6.5, and the clear liquid adds to the quarter as alkaline etch bath after chloride ion content is qualified in the clear liquid
In erosion machine；
(4) copper sludge recycles
Concentrated sulfuric acid dissolution is added in the copper sludge after mashing, forms copper sulphate mixed liquor, the copper sulphate mixed liquor is again
Crystallisation by cooling, dehydration separate up to technical grade sulfuric acid copper.
Pulping process: copper sulphate mother liquor is added in the copper sludge and is beaten, the concentration of copper sludge in copper sulphate mother liquor is controlled
For 45Be`, when the copper sulphate mother liquor deficiency, the concentration by the way that copper sludge described in water management is added is 45Be`.For example, reaction
Kettle is 2m3, copper sulphate mother liquor is first added in making beating, insufficient to add water polishing to 0.5m3, add copper sludge about 45Be` to making beating,
It is pumped into reaction kettle after the completion of mashing.
Concentrated sulfuric acid dissolution process: under the premise of stirring, the concentrated sulfuric acid is slowly added into reaction kettle, the concentrated sulfuric acid is reacted with copper
Copper sulphate is generated, when the concentration for the concentrated sulfuric acid that dissociates is 10g/L, reaction end is reached, stops that the concentrated sulfuric acid is added.
Crystallisation by cooling process: since the concentrated sulfuric acid is exothermic reaction with reacting for copper, when reaching reaction end, copper sulphate is mixed
The temperature for closing liquid rises to 90 DEG C, is passed through cold water from reaction kettle muff at this time, starts to crystallize as temperature reduces copper sulphate,
Copper sulphate mixed liquor is cooled to 30 DEG C~35 DEG C after 3 hours, stops logical cold water, completes crystallization.
Separation process: copper sulfate crystal is isolated with centrifuge dehydration, is technical grade after the copper sulfate crystal is dry
Copper sulphate, and the copper sulphate mother liquor on upper layer is collected for being beaten.
Compared with traditional extraction electrolysis method, present invention has the advantage that
Real zero-emission: it from watershed management, comprehensive utilization, loses copper waste liquid and is separated into clear liquid and copper sludge, clear liquid allotment
It returns to etching machine at fresh alkaline etching liquid to recycle, copper sludge is produced into technical grade sulfuric acid copper, and overall process does not have any waste
Discharge, thoroughly solves problem of environmental pollution；
Energy conservation is particularly evident: one ton of 2000 degree of copper loss electricity of electrolysis or more, the embodiment of the present invention is less than 200 degree；
Low in cost: on the basis of extracting 1 ton of copper, the cost of electrolysis method is 12000 yuan or more；The embodiment of the present invention is about
3000 yuan；
Economic benefit is obvious: it is equally subject to and extracts one ton of copper: 4 tons of copper sulphate of copper sludge energy output in the embodiment of the present invention,
Economic benefit occurred is much higher than electrolysis method；
Process is simple, and required equipment is few: equally with 10m3/ d is calculated.Extraction electrolysis method at least wants 3,000,000 yuan of costs
Investment；Investment of the embodiment of the present invention at most needs 700,000 yuan together with production copper sulphate equipment；
Also, the regeneration etching solution that the embodiment of the present invention is deployed is best in quality.
The foregoing is merely alternative embodiments of the invention, are not intended to limit the scope of the invention, all at this
Under the inventive concept of invention, using equivalent structure transformation made by description of the invention and accompanying drawing content, or directly/use indirectly
It is included in other related technical areas in scope of patent protection of the invention.
Claims (10)
1. a kind of alkalinity erosion copper waste liquor recovery process method of zero-emission, which comprises the following steps:
S1, hydrochloric acid is added into the erosion copper waste liquid of etching machine outflow, and the copper ammonia complexation ion that the hydrochloric acid makes to lose in copper waste liquid is broken
Network precipitating；
The erosion copper waste liquid of contact break precipitating is sent into equipment for separating liquid from solid, is isolated clearly by the equipment for separating liquid from solid by S2
Liquid and copper sludge；
Ammonia auxiliary agent is added in S3, Xiang Suoshu clear liquid, the clear liquid forms alkaline etch bath simultaneously by the way that the Ammonia auxiliary agent is added
It adds in the etching machine；
S4, the copper sludge are added concentrated sulfuric acid dissolution after mashing, prepare copper sulphate mixed liquor, the copper sulphate mixed liquor is cold again
But it crystallizes, dehydration separates up to technical grade sulfuric acid copper.
2. the alkalinity erosion copper waste liquor recovery process method of zero-emission as described in claim 1, which is characterized in that in S1 step
In, it is 3.5~6.5 that the hydrochloric acid, which is added, and adjusts the pH value of erosion copper waste liquid, and the copper ammonia complexation ion contact break for making to lose in copper waste liquid is heavy
It forms sediment.
3. the alkalinity erosion copper waste liquor recovery process method of zero-emission as described in claim 1, which is characterized in that in S2 step
In, the equipment for separating liquid from solid includes filter press, and the erosion copper waste liquid of contact break precipitating is pumped into the filter press, by described
Filter press isolates clear liquid and copper sludge.
4. the alkalinity erosion copper waste liquor recovery process method of zero-emission as described in claim 1, which is characterized in that in S3 step
In, the Ammonia auxiliary agent is one or both of ammonium hydroxide and ammonia, and the pH value that the Ammonia auxiliary agent adjusts the clear liquid is added
It is 9.5~11.5.
5. the alkalinity erosion copper waste liquor recovery process method of zero-emission as described in claim 1, which is characterized in that in S3 step
In, the concentration of chloride ion in the clear liquid is detected, the clear liquid forms alkaline quarter after the Concentration Testing of the chloride ion is qualified
Lose liquid.
6. the alkalinity erosion copper waste liquor recovery process method of zero-emission as described in claim 1, which is characterized in that in S4 step
In, it is 40Be`~50Be` that the concentration that copper sulphate mother liquor is beaten, and controls the copper sludge is added in Xiang Suoshu copper sludge.
7. the alkalinity erosion copper waste liquor recovery process method of zero-emission as claimed in claim 6, which is characterized in that when the sulfuric acid
When copper mother liquor deficiency, the concentration by the way that copper sludge described in water management is added is 40Be`~50Be`.
8. the alkalinity erosion copper waste liquor recovery process method of zero-emission as described in claim 1, which is characterized in that in S4 step
In, the concentrated sulfuric acid is added while stirring, when the concentration for the concentrated sulfuric acid that dissociates is 10g/L, stops the addition of the concentrated sulfuric acid.
9. the alkalinity erosion copper waste liquor recovery process method of zero-emission as described in claim 1, which is characterized in that in S4 step
In, the copper sulphate mixed liquor is cooled to 30 DEG C~35 DEG C in 3 hours, and copper sulphate completes knot in the copper sulphate mixed liquor
It is brilliant.
10. the alkalinity erosion copper waste liquor recovery process method of zero-emission as described in claim 1, which is characterized in that in S4 step
In, the copper sulphate mixed liquor of the crystallisation by cooling carries out dehydration separation using centrifuge, and the upper layer copper sulphate mother liquor after separation is used
In mashing.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111302472A (en) * | 2020-03-04 | 2020-06-19 | 惠州大亚湾亿田环保技术有限公司 | Zero-emission chlorate type acidic copper etching waste liquid treatment process |
| US20230166979A1 (en) * | 2021-11-30 | 2023-06-01 | Central South University | Method for treating copper-containing waste etching solution |
| WO2023208060A1 (en) * | 2022-04-26 | 2023-11-02 | 叶涛 | Method for recycling circuit board copper chloride etching waste liquid by means of precipitation treatment, and apparatus thereof |
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| CN108341424A (en) * | 2018-03-29 | 2018-07-31 | 东莞市恒建环保科技有限公司 | The production method of copper sulphate |
| CN109095642A (en) * | 2018-08-30 | 2018-12-28 | 惠州大亚湾亿田环保技术有限公司 | A kind of alkalinity erosion copper waste liquid environmental protection recovery process of zero-emission |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108341424A (en) * | 2018-03-29 | 2018-07-31 | 东莞市恒建环保科技有限公司 | The production method of copper sulphate |
| CN109095642A (en) * | 2018-08-30 | 2018-12-28 | 惠州大亚湾亿田环保技术有限公司 | A kind of alkalinity erosion copper waste liquid environmental protection recovery process of zero-emission |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111302472A (en) * | 2020-03-04 | 2020-06-19 | 惠州大亚湾亿田环保技术有限公司 | Zero-emission chlorate type acidic copper etching waste liquid treatment process |
| US20230166979A1 (en) * | 2021-11-30 | 2023-06-01 | Central South University | Method for treating copper-containing waste etching solution |
| US11939229B2 (en) * | 2021-11-30 | 2024-03-26 | Central South University | Method for treating copper-containing waste etching solution |
| WO2023208060A1 (en) * | 2022-04-26 | 2023-11-02 | 叶涛 | Method for recycling circuit board copper chloride etching waste liquid by means of precipitation treatment, and apparatus thereof |
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