CN100385023C - Copper recovering treatment process - Google Patents
Copper recovering treatment process Download PDFInfo
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- CN100385023C CN100385023C CNB2006100172164A CN200610017216A CN100385023C CN 100385023 C CN100385023 C CN 100385023C CN B2006100172164 A CNB2006100172164 A CN B2006100172164A CN 200610017216 A CN200610017216 A CN 200610017216A CN 100385023 C CN100385023 C CN 100385023C
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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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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The present invention relates to copper recovering treatment process and belongs to the field of chemical technology. The copper recovering treatment process includes three steps: the step of preparing sludge slurry with copper slime, copper containing sludge, waste acidic etching solution, etc; the step of reacting added hydroxide with sludge slurry to obtain reacted product solution; and the step of pressure filtering the reacted product solution to obtain solid copper oxide and filtrate. The present invention lowers the waste treating cost, raises operation safety and is favorable to environment protection.
Description
Technical field
The present invention and class, particularly a kind of copper recovering treatment process refers to a kind of copper recovering treatment process that is integrated in the makers' Waste Water Treatment of circuit card especially.
Background technology
As everyone knows, circuit card manufactory uses a large amount of metallic coppers; Making circuit card and lead frame process, steps such as etching and development can wash out the copper metal of part; In other words, have a large amount of valuable copper in the waste water of copper wiring factories such as circuit card or the waste liquid, copper in copper-containing wastewater, copper-contained sludge or the waste liquid must be converted into cupric oxide or copper hydroxide, there is usury the side with being worth, yet, at present do not have the recycling technology copper of copper-containing wastewater, copper-contained sludge or contained waste liquid effectively can be changed into cupric oxide or copper hydroxide as yet and do not have the problem of mud output simultaneously.So with economic point of view, need badly and develop a kind of technology that the copper of copper-containing wastewater, waste liquid and copper-contained sludge directly can be changed into cupric oxide or copper hydroxide, to improve the value of waste recycling, wastewater treatment end in factory solves mud output problem on the spot simultaneously, avoids the required cost of the outer processing of mud committee;
Along with development of science and technology and universalness, the related elements of electronic product, especially the output value of circuit card exceedance hundred billion elements, because its processing procedure uses a large amount of chemical agent and metallic substance, feasible waste liquid that is produced and waste are except containing multiple organic waste, more contain heavy metal ion such as a large amount of copper, lead and nickel, these plurality of heavy metal are if fail to deal carefully with, and will cause serious environmental to pollute and may jeopardize HUMAN HEALTH;
With the printed circuit board (PCB) manufacturing, meeting intermittence or continuous blow-down go out discarded tank liquor of all kinds of inorganic or organic high densitys and lower concentration Cleaning Wastewater in the production operation process; The discarded tank liquor of part high density belongs to strong acid or highly basic partially in the circuit card factory, and the heavy metal that contains high density in the waste liquid becomes to grade;
Present method of drawing waste liquid about Treatment of Copper waste water, nothing more than the raw wastewater that will take from circuit card manufactory discharging or waste liquid is dewatered and the neutralizing acid base number to reach legal emission standard, in other words, waste also can't be eliminated fully, only is to reduce the impact of waste for environment at most; For factory, processing waste water or waste liquid must be entrusted outer on behalf of processing, increase the running cost of factory on the other hand; Along with waste cumulative rises constantly, how to solve generation of waste materials or utilize waste fully again, make our limited living environment quality no longer be subjected to the threat of waste, the side is the very wise move of environment protection; Moreover, because the former material price of metal current is surging, reclaim if can will contain the metallic compound of these high economic worths, also can improve makers' earning capacity simultaneously;
At present the industry spininess carries out the research of recycling to each processing procedure waste water or waste, as the waste liquid that contains cupric oxide can utilize with basic solution and mix, and separates out cupric oxide; Reclaim cupric oxide from contain the chlorination copper waste etching solution, etching waste liquor and pH-value mix under 50 ℃ temperature more than or equal to 11 alkaline aqueous solution, and the cupric ion that is dissolved in the mixing solutions transforms into cupric oxide after sedimentation;
Being selected from sulfuric acid, nitric acid and hydrochloric acid etc. or multiple strong acid and height/superoxide (strong oxidizer) mixes with the copper-contained sludge of pbz polymer agglutinant, to carry out scission reaction, mix with the copper-contained sludge that disengages the pbz polymer agglutinant, to carry out scission reaction, to disengage the mixed solution of pbz polymer agglutinant and metallized metal oxychloride, the pH-value of adjusting mixed solution takes out polymer coagulant to acid, with after the remaining liquid furnishing alkalescence, isolate cupric oxide again; In addition, reclaim the method for copper from copper-contained sludge, also disclosed No. the 2118536th, No. the 6027543rd, United States Patent (USP), No. the 4670052nd, United States Patent (USP) and English Patent about utilizing strong acid and strong oxidizer; These technology are because the oxygenizement of strong oxidizer can produce the gas of a large amount of tool oxidation capacities, and therefore need set up scrubbing tower collects these gas, also can further recycle to avoid the personnel that endanger plant area.
Though there has been above-mentioned technology to recycle specific waste liquid, waste water or waste, but how above-mentioned technology or method only handle the discarded liquid or the waste of single processing procedure, copper waste etching solution, cupric chloride liquid or copper-contained sludge still fail to solve fully the pollution of other processing procedures; In addition, above-mentioned technology still can other waste liquid, waste water or the waste of output, and causes the expenditure of the outer processing costs of can't avoiding entrusting;
In the above-mentioned technology, still utilize cupric oxide for handling medicament, yet the price of the current former material of metal continues hurricane to rise, therefore utilize cupric chloride to face the progressively awkward situation of bed hedgehopping of cost for the copper recovery method of handling medicament, the copper recovery method of how seeking replacement scheme and reaching high benefit is the problem that industry presses for solution at present;
In addition, maximum person should belong to acid cupric cleaning waste liquid in each processing procedure waste liquid of printed circuit board (PCB) manufactory or the waste, but because its copper content is very low, only about 200ppm, so never be regarded as the object of copper recycling, yet its quantum of output is huge and pH-value is extremely low about more than 0.7, if it can be dealt carefully with, even helpful for the copper recycling, then significantly reduce the puzzlement of manufactory's wastewater treatment;
Therefore, need badly and want a kind of and solve at least a processing procedure waste liquid or waste reclaims problem and can reach the copper recovering treatment process that essence reduces the offal treatment cost.
Summary of the invention
The object of the present invention is to provide a kind of copper recovering treatment process, solved the problems such as recovery of acid contained waste liquid, copper-contained sludge and cupric scavenging solution etc. in existing printed circuit board (PCB) each processing procedure waste liquid of manufactory or the waste precious metals such as the pollution of environment and copper.
Technical scheme of the present invention comprises mud slurry preparation process, and a reactions steps reaches a press filtration step optionally;
In mud slurry preparation process, the composition of mud slurry preparation comprises a) a copper-contained sludge cake and/or a cupric thickened sludge, b) acid etching contained waste liquid, c) the acid cupric micro-etching solution of acid cupric micro-etching solution and stripping and hanging frame mixture, d) acid cupric rinse water waste liquid, wherein with composition a), b) and c) mix, or with composition a) with d) mixes, form a mud and starch; The pH-value of the mud slurry of gained is controlled at 2～6.99.
In reactions steps, add alkaline hydrated oxide, itself and this mud slurry is reacted, obtain a reaction product solution; The ratio of alkaline hydrated oxide and mud slurry is 1～2.5: 5.
After reactions steps, also comprise a press filtration step, with above-mentioned solution press filtration, obtain a solid and a filtered liquid; The solid of gained is a cupric oxide; Reacted at least 1 hour; The pH-value that the reaction generation solution of gained is finished in reaction is controlled at 8.5～9.5.
Used alkaline hydrated oxide comprises basic solutions such as NaOH, KOH in the reaction, and solid; The concentration of reacting used alkaline hydrated oxide is more than 20～90%; The pH-value of reactions steps is 9～13.
This filtered liquid is circulated back to the makers' Waste Water Treatment of circuit card, in order to adjust the alkalescence of original Waste Water Treatment waste water;
Mud slurry preparation process also comprises uses tap water and/or press filtration water;
Comprise also in the reactions steps that cupric chloride liquid is added the mud slurry to react with liquid caustic soda;
Press filtration water is back to reactions steps and/or is back to mud slurry preparation process;
Composition a) with composition b) c) part by weight is following copper-contained sludge cake and/or cupric thickened sludges of parts by weight, the acid etching contained waste liquid that two weight umbers are above, and following acid cupric micro-etching solution and the acid cupric micro-etching solution of the stripping and hanging frame mixture of parts by weight;
The copper-contained sludge cake of one parts by weight and/or the acid cupric rinse water waste liquid of a cupric thickened sludge and at least one parts by weight are stirred, form mud slurry;
Also comprise and add reactions steps containing the SPS acid waste liquid;
Sludge cake comprises sludge-drying.
Another object of the present invention is to provide a kind of copper recovery and processing system, it comprises at least:
One mud slurry preparation unit, wherein with a) a copper-contained sludge cake and/or a cupric thickened sludge, b) acid etching contained waste liquid and c) acid cupric micro-etching solution and stripping hold the acid cupric micro-etching solution of frame mixture and add and mix, or with a) copper-contained sludge cake and/or a cupric thickened sludge and a d) acid cupric rinse water waste liquid mixes, and forms mud slurry;
One reaction member is connected with this mud slurry preparation unit, wherein adds alkaline hydrated oxide, and itself and mud slurry are reacted, and obtains a reaction product solution;
This system also comprises the unitary press filtration of ligation unit.
The invention has the advantages that: need be by the oxidizing reaction of strong oxidizer, only need earlier sludge cake to be become the copper-contained sludge slurry that can stir, can directly form the reaction of cupric oxide, therefore not only do not need to bear the cost that strong oxidizer is bought, do not need to worry tool oxidation capacity gas critical HUMAN HEALTH of possibility and environmental safety and the problems such as collection and confinement of gases or recovery of deriving yet; Treating processes can not produce a large amount of smog, and the low pure strong acid of corrodibility is a lot, and therefore than treatment technology commonly used, heavy metal collection method of the present invention can obviously improve processing safety.
Description of drawings:
Fig. 1 to Fig. 3 is the synoptic diagram of copper recovery and processing system of the present invention.
Embodiment:
With the circuit board process is example, and its process unit comprises surface treatment, and etching resistance agent is shifted, after etching is shifted in etching resistance agent, goes etching resistance agent, and is black/brown oxidation, boring, de-smear, plated-through-hole, circuit copper facing, zinc-plated lead are shifted in anti-plating resistance agent, go anti-plating resistance agent and etching, divest tin lead, print anti-welding green lacquer, nickel plating is gold-plated and spray tin etc., and the process unit that wherein may produce contained waste liquid comprises etching (circuit card ectonexine), plated-through-hole and circuit copper facing;
The tank liquor composition that circuit card ectonexine etch process uses comprises iron(ic) chloride, cupric chloride, ammonium chloride and ammoniacal liquor, so the waste liquid that this processing procedure produces comprises waste liquids such as iron(ic) chloride, cupric chloride and ammonium chloride; Plated-through-hole comprises whole hole/adjustment, microetch, and activation, accelerationization and chemical copper deposition, wherein the microetch processing procedure uses sulfuric acid/hydrogen peroxide, Sodium Persulfate or ammonium persulphate; The copper ketone liquid that the chemical copper deposition manufacture process uses comprises mantoquita (copper sulfate), EDTA or tartrate sequestrant and sodium hydroxide pH-value control agent etc.
Printed circuit board (PCB) manufactory itself has a waste water treatment plant usually, and in order to handle waste liquid and the waste water from each processing procedure, wherein waste liquid and waste water comprise various heavy, for example copper, tin, lead and gold etc.; Collect to be about 2～3 from the pH-value of the mixed waste liquor of the waste liquid of each processing procedure, add and the pH-value of mixed waste liquor is heightened to alkalescence as materials such as iron(ic) chloride, be pH7～9, add polymer coagulant again and form thickened sludge, after the capable again press filtration, the solid of gained is the about sludge cake more than 70% of water content, and press filtration also is the discharge water for can directly discharging.
To dispose waste liquid in the system of the present invention originates comprises through spissated copper-contained sludge cake and/or cupric thickened sludge, copper content 〉=1%, the acid etching contained waste liquid that circuit card ectonexine etch process produces, copper content 〉=8%, the acid cupric micro-etching solution of the microetch that the microetch processing procedure produces, copper content 〉=0.1%, cupric solid-state castoff, high density strong acid waste liquid, thickened sludge, sludge cake and acid cupric rinse water waste liquid.
The cupric thickened sludge is to result from present circuit card manufactory the waste water of chemical copper processing procedure is fed an acidifying groove earlier to adjust pH-value to 2～3, adding iron(ic) chloride or multivalence aluminum chloride stirs, import the caustic dip groove again, make its pH-value be adjusted to pH-value 8～10 backs and form hydrogen-gasified thing suspension, again polymkeric substance is added, to quicken the suspension particle precipitation; The throw out that is deposited in the caustic dip trench bottom is pumped to thickener and is concentrated, and is pressed into through plate pressing machine at last that water content is about 70%, the cupric thickened sludge of copper content about 7%; Again upper strata liquid is gone after pH-value is adjusted groove to be adjusted to pH-value 6～9 again and release.
The acid etching contained waste liquid mainly contains cupric chloride, hydrogen peroxide and hydrogenchloride, and pH-value is less than 0.5;
Acid cupric micro-etching solution mainly contains hydrogen peroxide and sulfuric acid, and pH-value is less than 1.5;
The acid cupric micro-etching solution of stripping and hanging frame mainly comprises hydrogen peroxide and cupric nitrate, and pH-value is less than 1.3;
Use the high density strong acid solution in said all processing procedures of high density strong acid waste liquid finger mark printed circuit board and produce but as yet not with the high density strong acid waste liquid of other waste liquids dilutions, for example comprise the high density strong acid waste liquid that acid etching processing procedure and stripping and hanging frame processing procedure etc. produce, wherein strong acid comprises nitric acid, sulfuric acid and hydrochloric acid, the strong acid waste liquid also comprises copper-containing substance;
Said cupric solid-state castoff refers to the commit suicide side crops of plate processing procedure, the copper scrap paper tinsel of lamination process, the useless moulding rim charge of molding manufacture procedure and the solid cupric wastes such as useless plate of useless treating selvedge bits and product examine test;
Said liquid caustic soda is meant the about highly basic more than 45% of concentration, for example highly basic such as sodium hydroxide and potassium hydroxide liquid; In like manner, solid caustic soda is for example highly basic such as sodium hydroxide and potassium hydroxide solid; Above-mentioned liquid caustic soda can be by solid caustic soda behind the water-soluble or solution and get;
Said thickened sludge is meant that the mixed waste liquor of printed circuit board (PCB) wastewater trough adds polymer coagulant gained, its copper content about 1～3% under alkaline condition;
Said mud slurry is meant by sludge cake and acid cupric rinse water waste liquid and mixes and form, as long as wherein the concentration of mud slurry reaches and agitating vane can be stirred also can pump viscosity to reactive tank through pump; Thickened sludge also can add in this step, with copper content that improves the mud slurry and the purpose that reaches digestion thickened sludge amount;
Said sludge cake is meant the solid of thickened sludge gained after press filtration, its water content at least 70%, and copper content is about 7%, and pH-value is about 7.5～9; In like manner, sludge-drying is further the anhydrate solid of back gained of thickened sludge, and water content is about 10%, yet its copper content can double;
Said acid cupric rinse water waste liquid is meant the about 200ppm of copper content, and pH-value is more than 0.7, from a large amount of rinse water waste liquids that clean etching solution in the printed circuit board (PCB) etch process.
Be treated to example with adding of copper:
Provide a kind of copper recovering treatment process according to another object of the present invention, comprise that at least mud slurry preparation process, a reactions steps reach a press filtration step optionally;
In mud slurry preparation process, the composition of mud slurry preparation comprises a) a copper-contained sludge cake and/or a cupric thickened sludge, b) acid etching contained waste liquid, c) the acid cupric micro-etching solution of acid cupric micro-etching solution and stripping and hanging frame mixture, d) acid cupric rinse water waste liquid, wherein with composition a), b) and c) mix, or with composition a) with d) mixes, shape face one mud is starched.
When the present invention uses in reality, will be an amount of in the mud slurry preparation process, preferablely stir with the sludge cake of parts by weight and the acid cupric rinse water waste liquid of at least one parts by weight, form the mud slurry; Or the sludge-drying of parts by weight clayed into power, the acid cupric rinse water waste liquid that adds at least one parts by weight again stirs, and forms the mud slurry; The pH-value of the mud slurry of gained is controlled at 2～6.99.
Polymkeric substance in copper-contained sludge cake and/or the cupric thickened sludge can be resolved into suspended particulates by contained strong acid in the mixture of acid etching contained waste liquid and acid cupric micro-etching solution and the acid cupric micro-etching solution of stripping and hanging frame;
Wherein, mud slurry preparation process also comprises use tap water and/or press filtration water;
Sludge cake comprises the sludge-drying powder;
In reactions steps, the weight of liquid caustic soda accounts at least 17% of other reactant gross weights; This reaction is pyrogenic reaction, and temperature reaches at least 70 ℃, and the pH-value between the reaction period should be more than 12, can react to generate to contain the cupric oxide reaction product;
In reactions steps, add alkaline hydrated oxide, itself and mud slurry are reacted, obtain a reaction product solution;
The ratio of alkaline hydrated oxide and mud slurry is 1～2.5: 5; At least 1 hour reaction times;
Comprise also in the reactions steps that cupric chloride liquid is added the mud slurry to react with liquid caustic soda;
Composition a) with composition b) c) weight ratio is following copper-contained sludge cake and/or cupric thickened sludges of parts by weight, the acid etching contained waste liquid that two weight umbers are above, and following acid cupric micro-etching solution and the acid cupric micro-etching solution of the stripping and hanging frame mixture of parts by weight;
The copper-contained sludge cake of one parts by weight and/or the acid cupric rinse water waste liquid of a cupric thickened sludge and at least one parts by weight are stirred, form mud slurry;
Contain SPS acid waste liquid, nitric acid, sulfuric acid, liquid caustic soda and mud slurry are inserted and are reacted; In this situation, will contain SPS acid waste liquid, nitric acid and the sulfuric acid adding of the parts by weight more than totally 0.5 reactions steps, wherein the weight of liquid caustic soda accounts for and contains at least 17% of SPS acid waste liquid, nitric acid, sulfuric acid and mud slurry gross weight;
The SPS that contains in the SPS acid waste liquid is meant polystyrene (Syndiotatic PolyStyrene), and its fusing point has excellent heat resistance, chemical and electric property up to 270 ℃; This SPS acid waste liquid is different with the composition that is used for nitric acid of the present invention and sulfuric acid waste, contains for example interfacial agent etc.; Wherein said nitric acid and sulfuric acid can be commercially available industrial nitric acid and sulfuric acid, or use acidic solution to carry out the microetch processing procedure in all processing procedures of printed circuit board (PCB), for example black/brown oxidation, plated-through-hole, full plate copper facing, circuit copper facing and acid waste liquid that zinc-plated lead produced or above-mentioned high density strong acid waste liquid; The pH-value of acid etching waste liquid is about more than 0.3, mainly contains materials such as sulfuric acid, nitric acid, more than the about 200ppm of copper content; The high density strong acid waste liquid that preferable employing is above-mentioned, because not only can consume the waste liquid that is produced in the printed circuit board (PCB) manufactory, and high density strong acid waste liquid can not produce a large amount of smog in treating processes of the present invention, and it is a lot of that corrodibility is lower than pure strong acid, therefore can obviously improve processing safety.
According to alkaline hydrated oxide, the ratio that contains sodium hydroxide, potassium hydroxide, liquid caustic soda and solid base thereof etc. and mud slurry equals 1～2.5: 5, with alkaline hydrated oxide, contain sodium hydroxide, potassium hydroxide, liquid caustic soda and solid base thereof etc. and put into crystallization reaction groove C with the mud slurry of taking from the mud slurry storage tanks, the natural reaction temperature rises to about 80 ℃ approximately, stirring makes its reaction about at least 1 hour, preferable about 2 hours; Wherein, liquid caustic soda can be the alkaline hydrated oxide that the processing procedure of circuit card manufactory own uses, and contains sodium hydroxide, potassium hydroxide, liquid caustic soda and solid base thereof etc., for example basic solution such as NaOH, KOH; Alkaline hydrated oxide, the concentration that contains sodium hydroxide, potassium hydroxide, liquid caustic soda and solid base thereof etc. is more than 20～90%, is preferably 20～50%; In the reaction process, its pH-value 9～13 of preferable control, by pH-value monitor or sensor monitoring, in case find pH-value near 9 o'clock, the promptly an amount of at once raw material of taking from the raw material storage groove that adds is to keep the reaction conditions of pH-value 9～13;
The pH-value that the reaction generation solution of gained is finished in reaction is controlled at 8.5～9.5; The pH-value of reactant is reduced,, can heighten the usage quantity of liquid caustic soda in good time for the pH-value that makes reactant maintains more than 12; The pH-value that contains the cupric oxide reaction product that gained is finished in reaction should be controlled at 8.5～9.5, can utilize acid cupric rinse water waste liquid that reaction is finished after too high pH-value reduce in the desired pH-value scope;
After reactions steps, also comprise a press filtration step, with above-mentioned solution press filtration, obtain a solid and a filtered liquid; The solid of gained is a cupric oxide; Above-mentioned reaction product is carried out press filtration and is anhydrated, and obtains one and contains the cupric oxide solid, and its water content is about 50～70%, and its copper content accounts for that to contain the cupric oxide solid weight about more than 10%; Should be appreciated that gained contains the oxidation copper cake except that containing this any type of cupric oxide after the press filtration, and other metallic impurity are still arranged, the weight ratio that the interior alleged copper of present embodiment accounts for the cupric oxide solids is meant that the copper in the cupric oxide accounts for the weight percent of this solids;
This filtered liquid is circulated back to the makers' Waste Water Treatment of circuit card, in order to adjust the alkalescence of original Waste Water Treatment waste water; Press filtration water is back to reactions steps and/or is back to mud slurry preparation process.
Another object of the present invention, a kind of copper recovery and processing system is provided, at least comprise mud slurry preparation unit, wherein with a) a copper-contained sludge cake and/or a cupric thickened sludge, b) acid etching contained waste liquid and c) acid cupric micro-etching solution and the acid cupric micro-etching solution of stripping and hanging frame mixture adding mixing, or with a) copper-contained sludge cake and/or a cupric thickened sludge and a d) acid cupric rinse water waste liquid mixes, and forms mud slurry;
One reaction member is connected with this mud slurry preparation unit, wherein adds alkaline hydrated oxide, and itself and mud slurry are reacted, and obtains a reaction product solution;
Copper recovery and processing system of the present invention comprises that also one connects the press filtration unit of this reaction member;
Copper recovery and processing system of the present invention comprises the mud slurry preparation unit that connects in regular turn at least, a reaction member and a press filtration unit, and optionally connect unitary drying unit of a press filtration and the unitary grinding unit of a connection mud slurry preparation;
Connect mud slurry preparation unit, reaction member and press filtration unit and connect used pipeline, its material must be strong alkali-acid resistance, its caliber is decided on handling tonnage, only otherwise can block pipeline easily get final product, its length is then decided on the relation far and near and that each cell position disposes of on-the-spot each processing procedure waste liquid/waste outlet.
As shown in Figure 1, be a specific embodiment according to the present invention, a kind of synoptic diagram of copper recovery and processing system; Copper recovery and processing system of the present invention comprises mud slurry preparation unit A, a reaction member B and a press filtration unit C;
Acid etching contained waste liquid, copper-contained sludge cake and/or cupric thickened sludge, and the mixture of the acid cupric micro-etching solution of acid cupric micro-etching solution and stripping and hanging frame respectively via an acid etching contained waste liquid 2, a copper-contained sludge cake and/or cupric thickened sludge pipe 1, and the mixing property management 3 of an acid cupric micro-etching solution and the acid cupric micro-etching solution of stripping and hanging frame adds mud slurry preparation unit A;
Above-mentioned acid etching contained waste liquid, copper-contained sludge cake and/or cupric thickened sludge, and the mixture of the acid cupric micro-etching solution of acid cupric micro-etching solution and stripping and hanging frame stir up to thick copper-contained sludge cake and/or cupric thickened sludge and resolve into the mud slurry that can be stirred;
Also can be provided with one in addition and comprise that mud slurry storage tanks connects mud slurry preparation unit A, standby in order to the mud slurry that stores gained;
Mud slurry preparation unit A also can be provided with the liquid line of an input in order to regulon content pH-value in addition, as water/pressing filtering liquid pipe;
The mud slurry imports reaction member B through a dirty mud tube 4; Beyond the scrubbing mud tube 4, reaction member comprises a liquid caustic soda pipe 5 and a reaction product pipe 7 at least; Also comprise monochlor(in)ate copper sewer pipe 6; Also can optionally import liquid line, as water/press filtration pipe in order to conditioned reaction substrate concentration and/or pH-value;
The discharge end of press filtration unit C can comprise a solid lines P and a filtered liquid pipeline L, wherein filtered liquid pipeline L is connected in the makers' Waste Water Treatment of circuit card, mud slurry preparation unit A or reaction member B, in order to the concentration and/or the pH-value of adjustment unit content.
According to another object of the present invention, the copper recovery and processing system comprises that a sludge cake and acid cupric rinse water waste liquid insert to mix in the mud slurry preparation unit and forms a mud and starch; Mud slurry preparation unit comprises that at least one is provided with the steel basin of agitator, can comprise optionally that also one connects the mud slurry storage tank of steel basin, in order to store the mud slurry that forms in the agitator;
Containing SPS acid waste liquid, nitric acid, sulfuric acid, liquid caustic soda and mud slurry can import reaction member separately respectively through its corresponding pipeline, and also can suitably go ahead of the rest to mix imports again; For example contain the SPS acid waste liquid, nitric acid and sulfuric acid may be from high density strong acid waste liquids, but therefore Jing imports high density strong acid waste liquid through a corresponding pipeline, react with liquid caustic soda and mud slurry in reaction member; Or other establishes some storage tanks, contains the SPS acid waste liquid in order to storage respectively, and strong acid and liquid caustic soda are with the flow in the stable input reaction member; Also can be provided with one in addition and contain cupric oxide reaction product storage tanks, contain the cupric oxide reaction product solution in order to depot reaction unit output;
Contain the cupric oxide reaction soln and carry out press filtration through reaction soln pipe importing press filtration unit, obtain one and contain oxidation copper cake and a press filtration water from reaction member; The press filtration unit can connect a drying unit in addition, in order to the above-mentioned oxidation copper cake that contains of drying;
Owing to add a large amount of liquid caustic soda in the reaction member, for reducing the pH-value in the groove, can set up an acid cupric rinse water sewer pipe, the acid cupric rinse water waste liquid input reactive tank that above-mentioned pulp step is used is with the pH-value in the control reactive tank;
As shown in Figure 2, be another specific embodiment according to the present invention, a kind of synoptic diagram of copper recovery and processing system; It comprises mud slurry preparation unit A, a reaction member B and a press filtration unit C;
Mud slurry preparation unit A comprises a sludge cake conveying belt 10, one acid cupric rinse water sewer pipes 20 and mud slurry transfer lime 30; Mud slurry preparation unit A comprises a steel basin and mud slurry storage tanks, wherein steel basin connects sludge cake conveying belt 10 and acid cupric rinse water sewer pipe 20, and mud slurry storage tank connects mud slurry transfer lime 30, and starches storage tank at agitator and mud and be provided with a pipe connecting and be connected each other;
When preparation mud slurry, be stirred smoothly for making sludge cake, can earlier acid cupric rinse water sewer pipe 20 be opened, acid cupric rinse water waste liquid is imported agitator earlier, open sludge cake conveying belt 10 again, sludge cake is imported agitator; Acid cupric rinse water waste liquid also can be the press filtration water of press filtration unit C output;
Mud slurry transfer lime 30 the other end ligation unit B; Reactive tank also is connected to a liquid caustic soda input tube 40, and contains SPS acid waste liquid input tube 50, one nitric acid input tubes, 60, one sulfuric acid input tubes 70 and and contain cupric oxide reaction product output tube 90 except that being connected to mud slurry transfer lime 30;
Reaction member B comprises a reactive tank at least, and wherein the preferable agitator that is provided with in the reactive tank is even in order to reaction; What reaction member B also can comprise a ligation groove contains cupric oxide reaction product storage tank;
Comprise reactive tank and contain in the situation of cupric oxide reaction product storage tank at reaction member B, reactive tank connects mud slurry transfer lime 30, liquid caustic soda input tube 40, contain SPS acid waste liquid input tube 50, nitric acid input tube 60 and sulfuric acid input tube 70, contain cupric oxide reaction product storage tank and connect and to contain cupric oxide reaction product output tube 90, reactive tank has a pipeline to be connected each other with containing between the cupric oxide reaction product storage tank; Optionally can set up a water pipe and/or filtered liquid pipe coupling reactive tank B, in time to adjust reactant concn and/or the pH-value in the reactive tank;
The mud slurry is through mud slurry transfer lime 30, and liquid caustic soda contains the SPS acid waste liquid through containing SPS acid waste liquid input tube 50 through liquid caustic soda input tube 40, nitric acid is through nitric acid input tube 60, sulfuric acid is inserted reactive tank through sulfuric acid input tube 70, after one section predetermined reaction time, forms the liquid cupric oxide reaction product that contains; Because reaction process can be disengaged reaction heat, the temperature of entire reaction unit B is reached more than 70 ℃, therefore can send into and contain cupric oxide reaction product storage tank containing the cupric oxide reaction product, leave standstill cooling after, deliver to press filtration unit C via containing cupric oxide reaction product output tube 90 again;
Press filtration unit C can be the device that utilizes pressure to carry out solid-liquid separation commonly used, for example plate pressing machine etc.; The pressure of operation is more than at least 6 kilograms; Press filtration unit C comprises that one contains a cupric oxide solid output terminal 100 and a press filtration water delivery pipe 110; Containing the cupric oxide reaction product obtains one and contains cupric oxide solid and a press filtration water after press filtration; Containing the cupric oxide solid takes out through containing cupric oxide solid output terminal 100; Press filtration water can be back to reaction member B as the usefulness of adjusting concentration in the reactive tank through press filtration water delivery pipe 110, or being back to waste water treatment plant's pH-value adjusts the alternative part liquid caustic soda use in pond.
As shown in Figure 3, be the another specific embodiment according to the present invention, a kind of structural representation of copper recovery and processing system; It comprises mud slurry preparation unit A, a reaction member B and a press filtration unit C;
Mud slurry preparation unit A comprises a sludge cake conveying belt 10, one acid cupric rinse water sewer pipes 20 and mud slurry transfer lime 30; Mud slurry preparation unit A comprises a steel basin and mud slurry storage tank, wherein steel basin connects sludge cake conveying belt 10 and acid cupric rinse water sewer pipe 20, and mud slurry storage tank connects mud slurry transfer lime 30, and starches storage tank at agitator and mud and be provided with a pipe connecting and be connected each other;
Mud slurry transfer lime 30 the other end ligation unit B; Reactive tank also is connected to a liquid caustic soda input tube 40, one mixture input tubes 80 and and contains cupric oxide reaction product output tube 90 except that being connected to mud slurry transfer lime 30;
Mud slurry preparation unit A can optionally import in order to the concentration of regulon content and/or the liquid line of pH-value, as water/pressing filtering liquid pipe;
Reaction member B comprises a reactive tank at least, and wherein the preferable agitator that is provided with in the reactive tank is even in order to reaction; What reaction member B also comprised a ligation groove contains cupric oxide reaction product storage tank;
Comprise reactive tank and contain in the situation of cupric oxide reaction product storage tank at reaction member B, reactive tank connects mud slurry transfer lime 30, liquid caustic soda input tube 40, mixture input tube 80, contain cupric oxide reaction product storage tank and then connect and contain cupric oxide reaction product output tube 90, reactive tank has a pipeline to be connected each other with containing between the cupric oxide reaction product storage tank; Optionally can set up one water pipe/filtered liquid pipe coupling reactive tank B, in time to adjust reactant concn and/or the pH-value in the reactive tank;
Mud slurry is through mud slurry transfer lime 30, and liquid caustic soda contains SPS acid waste liquid, nitric acid and sulfuric acid and inserts reactive tank through mixture input tube 80 through liquid caustic soda input tube 40, after one section predetermined reaction time, forms the liquid cupric oxide reaction product that contains; Because reaction process can be disengaged reaction heat, the temperature of entire reaction unit B is reached more than 70 ℃, therefore can send into and contain cupric oxide reaction product storage tank containing the cupric oxide reaction product, leave standstill cooling after, deliver to press filtration unit C via containing cupric oxide reaction product output tube 90 again;
Press filtration unit C can be the device that utilizes pressure to carry out solid-liquid separation commonly used, for example plate pressing machine etc.; The pressure of operation is more than at least 6 kilograms; Press filtration unit C comprises that one contains a cupric oxide solid output terminal 100 and a press filtration water delivery pipe 110; Containing the cupric oxide reaction product obtains one and contains cupric oxide solid and a press filtration water after press filtration; Containing the cupric oxide solid takes out through containing cupric oxide solid output terminal 100; Press filtration water can be back to reaction member B as the usefulness of adjusting concentration in the reactive tank through press filtration water delivery pipe 110, or being back to waste water treatment plant's pH-value adjusts the alternative part liquid caustic soda use in pond;
Said input tube, output tube, transfer lime or conveying belt are meant pipeline or pipeline or other e Foerderanlages of delivering liquid or solid matter; Via separately control unit, for example control valve or controller etc. are carried tie substance in the corresponding unit with manual or automatization mode, to control desired pH-value and proportioning etc. in each unit respectively for above-mentioned all pipelines or transfer lime.
1000 kilograms acid cupric rinse water waste liquids and 1000 kilograms of cupric thickened sludges are inserted mud slurry preparation unit A, stir, form copper-contained sludge slurry.
With 650 kilograms of liquid caustic soda, 600 kilograms contain SPS acid waste liquid, nitric acid and sulfuric acid mixture, and the copper-contained sludge of above-mentioned gained slurry is added in the reaction member; After reaction is finished, after will containing the cupric oxide reaction product and delivering to the press filtration unit and carry out press filtration and drying, obtain about 480 kilograms of cupric oxide solids and about 2755 kilograms press filtration water, wherein to account for the weight percent of this cupric oxide solids be about 20% to cupric oxide.
With 1200 kilograms acid cupric rinse water waste liquid, 500 kilograms of copper-contained sludge cakes and the powder of 500 kilograms of cupric sludge-dryings after grinding are inserted mud slurry preparation unit A, stir, and form copper-contained sludge slurry;
With 800 kilograms of liquid caustic soda, 1000 kilograms contain SPS acid waste liquid, nitric acid and sulfuric acid mixture, and the copper-contained sludge of above-mentioned gained slurry is added in the reaction member; After reaction is finished, after will containing the cupric oxide reaction product and delivering to the press filtration unit and carry out press filtration and drying, obtain about 375 kilograms of cupric oxide solids and about 3220 kilograms press filtration water, wherein to account for the weight percent of this cupric oxide solids be about 40% to cupric oxide.
Acid etching contained waste liquid with 400 gram copper contents 10%, the cupric thickened sludge of 100 gram copper contents 7%, and 100 the gram copper contents 2% acid cupric micro-etching solution and 100 the gram cupric nitrates mixtures mix after, adding 245 grams, 45% sodium hydroxide reacted about 2 hours, with the press filtration of reaction soln process, obtain about 780 the gram filtered liquids and about 158 the gram contain the cupric oxide solids, the copper content that wherein contains the cupric oxide solids is 32%, water content is 55%; Filtered liquid comprises NaCl, Na
2SO
4, NaNO
3And H
2O.
4000 kilograms acid etching waste liquids and 1000 kilograms of copper-contained sludge cakes are added a steel basin, stir, form copper-contained sludge slurry;
With 600 kilograms of liquid caustic soda, it is in 15 tons the reactive tank that the copper-contained sludge of 1000 kilograms of cupric chloride liquid and 5000 kilograms of gained slurry is added in a capacity, after reacting, reaction product is delivered to the press filtration unit, obtain about 384 kilograms of cupric oxide solids and about 6100 kilograms press filtration water, wherein to account for the weight percent of this cupric oxide solids be 40% to copper.
4000 kilograms tap water and press filtration water mixed liquid and 1000 kilograms of copper-contained sludge cakes are added a steel basin, stir, form copper-contained sludge slurry;
With 600 kilograms of liquid caustic soda, it is in 15 tons the reactive tank that the copper-contained sludge of 1000 kilograms of cupric chloride liquid and 5000 kilograms of gained slurry adds a capacity, after reacting, reaction product is delivered to the press filtration unit, obtain about 540 kilograms of cupric oxide solids and about 6020 kilograms press filtration water, wherein to account for the weight percent of this cupric oxide solids be 26% to copper.
Embodiment 6
3500 kilograms acid etching waste liquids, 500 kilograms of press filtration water and 1000 kilograms of copper-contained sludge cakes are added a steel basin, stir, form copper-contained sludge slurry;
With 600 kilograms of liquid caustic soda, it is in 15 tons the reactive tank that the copper-contained sludge of 1000 kilograms of cupric chloride liquid and 5000 kilograms of gained slurry is added in a capacity, after reacting, reaction product is delivered to the press filtration unit, obtain about 476 kilograms of cupric oxide solids and about 6080 kilograms press filtration water, wherein to account for the weight percent of this cupric oxide solids be 32% to copper.
Embodiment 7
1000 kilograms acid cupric rinse water waste liquids and 1000 kilograms of copper-contained sludge cakes are inserted mud slurry preparation unit A, stir, form copper-contained sludge slurry;
With 650 kilograms of liquid caustic soda, 600 kilograms contain SPS acid waste liquid, nitric acid and sulfuric acid mixture, and the copper-contained sludge of above-mentioned gained slurry is added in the reaction member; After reaction is finished, after will containing the cupric oxide reaction product and delivering to the press filtration unit and carry out press filtration and drying, obtain about 480 kilograms of cupric oxide solids and about 2755 kilograms press filtration water, wherein to account for the weight percent of this cupric oxide solids be about 20% to cupric oxide.
Embodiment 8
With 1200 kilograms acid cupric rinse water waste liquid, 500 kilograms of copper-contained sludge cakes and the powder of 500 kilograms of cupric sludge-dryings after grinding are inserted mud slurry preparation unit A, stir, and form copper-contained sludge slurry;
With 800 kilograms of liquid caustic soda, 1000 kilograms contain SPS acid waste liquid, nitric acid and sulfuric acid mixture, and the copper-contained sludge of above-mentioned gained slurry is added in the reaction member; After reaction is finished, after will containing the cupric oxide reaction product and delivering to the press filtration unit and carry out press filtration and drying, obtain about 375 kilograms of cupric oxide solids and about 3220 kilograms press filtration water, wherein to account for the weight percent of this cupric oxide solids be about 40% to cupric oxide.
As from the foregoing, copper recovery and processing system of the present invention, output mud not only, and all are to take from the used medicament of manufactory itself in order to medicaments of handling copper and reclaiming, for example compound that spent acid or resource reutilization produced of liquid caustic soda, the output of manufactory own; Therefore utilize copper recovery and processing system Treatment of Copper waste water of the present invention or waste liquid, not only do not have the cost of buying more medicament, and handle the resulting compound in back, for example cupric oxide can become the profit product, fully improves the value of resource reutilization; The more important thing is that manufactory directly is integrated in copper recovery and processing system of the present invention waste water outlet end in this factory, can in factory, handle four kinds of waste water or waste liquid simultaneously, for the outer practice of handling of paying committee of present manufactory, not only significantly reduce the offal treatment cost of manufacturer, and can increase the operation profit simultaneously again, also help HUMAN HEALTH and environmental safety.
Claims (10)
1. copper recovering treatment process, it is characterized in that: this method comprises three steps, the one, mud slurry preparation process; The 2nd, reactions steps; The 3rd, the press filtration step; Wherein in mud slurry preparation process, the composition of mud slurry preparation comprises a) a copper-contained sludge cake and/or a cupric thickened sludge, b) acid etching contained waste liquid, c) the acid cupric micro-etching solution of acid cupric micro-etching solution and stripping and hanging frame mixture, d) acid cupric rinse water waste liquid, above-mentioned a), b), c), d) four kinds of waste liquids can with composition a), b) and c) mix; Or with composition a) with d) mix, form mud slurry, the pH-value of the mud slurry of gained is controlled at 2～6.99; In reactions steps, add alkaline hydrated oxide, itself and this mud slurry is reacted, obtain a reaction product solution, wherein the preparation ratio of alkaline hydrated oxide and mud slurry is 1～2.5: 5, pH-value 9～13, the reaction times is 1 hour; After reactions steps, be the press filtration step, the press filtration step is the reaction product solution press filtration that reactions steps is obtained, and obtains a solid and a filtered liquid, the gained solid is a cupric oxide.
2. copper recovering treatment process according to claim 1 is characterized in that: used alkaline hydrated oxide comprises NaOH or KOH basic solution and solid thereof in the said reaction.
3. copper recovering treatment process according to claim 1 is characterized in that: the concentration of the used alkaline hydrated oxide of said reactions steps is 20～90%.
4. copper recovering treatment process according to claim 1 is characterized in that: comprise the use tap water in the said mud slurry preparation process.
5. copper recovering treatment process according to claim 1 is characterized in that: comprise in the said reactions steps that cupric chloride liquid is added the mud slurry to react with liquid caustic soda.
6. copper recovering treatment process according to claim 1 is characterized in that: the press filtration water in the said press filtration step is back to reactions steps, or is back to the mud preparation process.
7. copper recovering treatment process according to claim 1, it is characterized in that: comprise in the said reactions steps and reacting containing SPS acid waste liquid, nitric acid, sulfuric acid and liquid caustic soda adding mud slurry, wherein, containing SPS acid waste liquid, nitric acid and vitriolic parts by weight is 0.5.
8. copper recovering treatment process according to claim 7 is characterized in that: the weight of liquid caustic soda accounts for and contains at least 17% of SPS acid waste liquid, nitric acid, sulfuric acid and mud slurry gross weight.
9. copper recovery and processing system, at least comprise mud slurry preparation unit, wherein with a) a copper-contained sludge cake and/or a cupric thickened sludge, b) acid etching contained waste liquid and c) acid cupric micro-etching solution and the acid cupric micro-etching solution of stripping and hanging frame mixture adding mixing, or with a) copper-contained sludge cake and/or a cupric thickened sludge and a d) acid cupric rinse water waste liquid mixes, and forms mud slurry;
One reaction member is connected with this mud slurry preparation unit, wherein adds alkaline hydrated oxide, and itself and this mud slurry is reacted, and obtains a reaction product solution.
10. copper recovery and processing system according to claim 9 is characterized in that: this system comprises the unitary press filtration of ligation unit.
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| JP4199821B1 (en) * | 2008-01-15 | 2008-12-24 | 株式会社荏原製作所 | Method and apparatus for removing and recovering copper from copper-containing acidic waste liquid |
| CN102303917B (en) * | 2011-08-25 | 2014-01-01 | 石祥阁 | Method for mixed treatment of waste liquid from acid etching and micro etching of printed circuit boards |
| CN102432093A (en) * | 2011-11-15 | 2012-05-02 | 镇江市电器设备厂有限公司 | Treatment device and treatment method for copper conductor acid washing waste liquid |
| CN104313331B (en) * | 2014-09-28 | 2016-08-24 | 江苏中容铜业有限公司 | A kind of method reclaiming copper junk |
| CN112266094A (en) * | 2020-09-25 | 2021-01-26 | 陕西汉和新材料科技有限公司 | Electrolytic copper foil washing water treatment method |
| CN112941562A (en) * | 2021-01-13 | 2021-06-11 | 湖南埃格环保科技有限公司 | Combined treatment method for copper-containing sludge and copper-containing etching waste liquid |
| CN114195315A (en) * | 2021-12-30 | 2022-03-18 | 江苏维达环保科技有限公司 | Method for combined treatment of acidic and non-acidic copper-containing etching waste liquid, tin stripping waste liquid and copper nitrate waste liquid |
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| CN1312391A (en) * | 2001-02-21 | 2001-09-12 | 谢祯辉 | Method of recovering metal from metal-containing sludge |
| JP2002018395A (en) * | 2000-07-06 | 2002-01-22 | Taiheiyo Cement Corp | Treating method for waste |
| CN1396281A (en) * | 2002-06-21 | 2003-02-12 | 清华大学 | Process for recovering metal and non-metal materials from copper enriched electronic waste |
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| JP2002018395A (en) * | 2000-07-06 | 2002-01-22 | Taiheiyo Cement Corp | Treating method for waste |
| CN1312391A (en) * | 2001-02-21 | 2001-09-12 | 谢祯辉 | Method of recovering metal from metal-containing sludge |
| CN1396281A (en) * | 2002-06-21 | 2003-02-12 | 清华大学 | Process for recovering metal and non-metal materials from copper enriched electronic waste |
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