CN103979755A - Comprehensive treatment method of electro-plating sludge and sludge containing low amount of copper - Google Patents
Comprehensive treatment method of electro-plating sludge and sludge containing low amount of copper Download PDFInfo
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- CN103979755A CN103979755A CN201410227715.0A CN201410227715A CN103979755A CN 103979755 A CN103979755 A CN 103979755A CN 201410227715 A CN201410227715 A CN 201410227715A CN 103979755 A CN103979755 A CN 103979755A
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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 invention provides a comprehensive treatment method of electro-plating sludge and sludge containing low amount of copper. The method comprises the steps of step a, mixing the electro-plating sludge and the sludge containing low amount of copper to be treated to prepare sludge dry slag by virtue of a sludge drier; step b, putting the sludge dry slag into an electrolyte preparation tank, adding an appropriate amount of dilute sulfuric acid, and fully stirring to obtain a first heavy metal electrolytic solution; step c, putting the sludge dry slag which is not dissolved in the electrolyte preparation tank into a centrifuge, and separating to obtain sludge centrifugal dry slag and a second heavy metal electrolytic solution; step d, putting the first heavy metal electrolytic solution and the second heavy metal electrolytic solution into an electrolytic tank to form an electrolyte, and performing continuous heating and continuous electrolysis on the electrolyte to generate a high-purity mixed metal electrolysis plate. According to the comprehensive treatment method provided by the invention, the heavy metal content in the treated sludge can achieve the standard, and mixed metal electrolysis plate products with very high purity can be further generated; the comprehensive treatment method has quite significant economic and social benefits.
Description
[technical field]
The present invention relates to printed-board technology field, especially relate to a kind of electroplating sludge and low amount copper-contained sludge integrated conduct method.
[background technology]
In recent years along with the fast development of electron trade, the annual growth rate that always keeps 10-20% as electronic industry basic link-printed electronic circuit board industry, the current domestic family more than 3500 of printed circuit board manufacturing enterprise that has multiple scale, monthly output reaches 1.2 hundred million square metres.
In the manufacturing processed of printed circuit board, need to consume a large amount of smart copper, according to incompletely statistics, China's year row's electroplating wastewater approximately 6,000,000,000 m
3left and right.Electroplate Factory mostly scale is less and disperse, and technology is relatively backward, and the overwhelming majority be take copper facing, zinc, nickel and chromium as main.Process at present electroplating wastewater and adopt chemical precipitation method more, therefore in treating processes, can produce the electroplating sludge of plurality of heavy metal.This electroplating sludge contains various metals composition, and character is complicated, is one of generally acknowledged both at home and abroad public hazards.
Electroplating sludge is administered with the method for comprehensive utilization can be divided into four classes:
1, make electroplating sludge stabilization, its harm to environment is dropped to minimum, and do not reclaim metal wherein.The main solidifying agent that adopts solidifies, stablize after electroplating sludge, then carries out landfill, fill out sea or stack processing, and the metal in mud is wasted, and has caused resource loss.
2. pair electroplating sludge fully utilizes, and adopts a series for the treatment of measures, electroplating copper-contained sludge, is processed into the Industrial materials such as material of construction, modified plastics, tanning agent.Metal in mud is wasted, and has caused resource loss.
3, adopt multiple physics and chemical treatment method, just the copper in mud is extracted to the final form with metallic copper or mantoquita and reclaim, realize the recycling of electroplating sludge.In the method, mud, after certain pre-treatment, adopts ammoniacal liquor, sulfuric acid or ferric sulfate to leach the copper in mud.It is good that ammoniacal liquor leaches selectivity, but ammoniacal liquor has irritating smell, higher to leaching device sealing requirements.The volatilization of ammoniacal liquor is more, will cause the loss of ammoniacal liquor and the deterioration of operating environment; The sulfuric acid leaching reaction times is shorter, and efficiency is higher, but sulfuric acid has stronger corrodibility, higher to reactor requirement for anticorrosion; The leaching efficiency of ferric sulfate is higher, but the reaction times is longer, therefore needs larger reactor volume.And in the method mud, other heavy metal does not propose, and has caused the wasting of resources.
4, electroplating sludge burns solidify & bury treatment technology, this technology adopts a series of means to process electroplating sludge, make heavy metal wherein no longer environment be produced and be polluted, the electroplating sludge containing plurality of heavy metal is processed very effective, but fail reuse heavy metal wherein, cause the waste of resource.
For electroplating sludge treatment process, to environment, can cause great harm above, not reach electric plating sludge resource utilization.What low amount copper-contained sludge existing market was used is directly to smelt with smelting furnace, in smelting process, can produce a large amount of pollutents, and environment has been produced to great harm, does not reach copper-contained sludge recycling.
And low amount copper-contained sludge existing market treatment process: reclaim unit low amount copper-contained sludge is reclaimed, the copper-contained sludge of retrieving is made to fritter shape individuality to be placed under the sun and to dry, copper-contained sludge after drying is put into copper smelting furnace and is got copper, smelt like this and get copper method and have in process of production part copper and lose, caused the wasting of resources, smelting furnace can produce a large amount of dusty gass in operation, in order to save the mud that cost recovery unit gets after copper, generally can be dropped, environment is caused to great harm.
[summary of the invention]
The technical problem to be solved in the present invention is, defect for prior art, a kind of electroplating sludge and low amount copper-contained sludge integrated conduct method are provided, and not only making to process rear Of Heavy Metal Level In Sludge can be up to standard, more can produce the hybrid metal electrolytic zinc-coated steel sheet that purity is very high.
In order to solve the problems of the technologies described above, the invention provides a kind of electroplating sludge and low amount copper-contained sludge integrated conduct method, said method comprising the steps of:
Step a: pending electroplating sludge is mixed and added in sludge drying machine with low amount copper-contained sludge, organism by sludge drying machine in 950 ~ 1000 ° of C removal mud and the flammable impurity in mud, obtain the dry slag of mud, and make the moisture control of the dry slag of described mud below 5%;
Step b: the dry slag of described mud is prepared to pond with putting into electrolytic solution after the encapsulation of glass cloth bag, toward described electrolytic solution, prepare pond and add appropriate dilute sulphuric acid, fully stir, heavy metal in the dry slag of described mud is dissolved in completely and in dilute sulphuric acid, obtains the first heavy metal electrolytic solution;
Step c: electrolytic solution is prepared in pond to the dry slag of undissolved mud and put into whizzer and carry out separation, obtain the centrifugal dry slag of mud and the second heavy metal electrolytic solution;
Steps d: described the first heavy metal electrolytic solution obtaining and the second heavy metal electrolytic solution are positioned over and form electrolytic solution in electrolyzer, by described electrolytic solution continuous heating to 40 ~ 45 ° C, and continue electrolysis with the current density of 0.5 ~ 1.0ASD, generate highly purified hybrid metal electrolytic zinc-coated steel sheet.
Further, in above-mentioned electroplating sludge and low amount copper-contained sludge integrated conduct method, described step b specifically comprises:
The dry slag of described mud is packaged into dry slag bag the unsettled electrolytic solution that is fixed on glass cloth bag to be prepared in the inner frame of pond, detect the heavy metal content in described dry slag bag, according to this heavy metal content, prepare appropriate dilution heat of sulfuric acid, toward described electrolytic solution, prepare and in pond, add described appropriate dilute sulphuric acid, by heating rod, electrolytic solution is prepared to solution in pond and be heated to 40 ~ 45 ° of C, fully stir and also by the drum machine of supporting, to described electrolytic solution, prepare in pond bulging fosterly, heavy metal in the dry slag of described mud is dissolved in completely and in dilute sulphuric acid, obtains the first heavy metal electrolytic solution.
Further, in above-mentioned electroplating sludge and low amount copper-contained sludge mixed processing method, described step c also comprises: the centrifugal dry slag of described mud is carried out to the processing of mummification disacidify by sludge drying machine, and the dry slag of described disacidify mud can be used for preparation and solidifies non-burning brick.
Further, in above-mentioned electroplating sludge and low amount copper-contained sludge integrated conduct method, the water ratio of the dry slag of described disacidify mud is below 5%.
Further, in above-mentioned electroplating sludge and low amount copper-contained sludge mixed processing method, after described steps d, also comprise: liquid after the electricity after electrolysis is added into described electrolytic solution and prepares in pond, be cycled to repeat described step b to steps d.
Mud after electroplating sludge of the present invention and low amount copper-contained sludge integrated conduct method are not only processed can be processed into non-burning brick product, more there is the very high hybrid metal electrolytic zinc-coated steel sheet product of the purity of generation, value, far above common electroplating sludge on market and low amount copper-contained sludge treatment process, has quite significantly economic benefit and social benefit.
[embodiment]
Below in conjunction with specific embodiment, electroplating sludge of the present invention and low amount copper-contained sludge integrated conduct method are described.
Embodiment 1:
Pending electroplating sludge is mixed and added in sludge drying machine with low amount copper-contained sludge, by sludge drying machine, at 1000 ° of C, go down except the flammable impurity in the organism in mud and mud, obtain the dry slag of mud, and make the moisture control of the dry slag of described mud below 5%, the dry slag of such mud is convenient to subsequent disposal;
The dry slag of described mud is placed on to dry place with glass cloth bag by 10 kilograms of every bag of encapsulation pending, again the unsettled electrolytic solution that is fixed on of dry slag bag after encapsulation is prepared in the inner frame of pond, detect the heavy metal content in described dry slag bag, according to this heavy metal content, prepare appropriate dilution heat of sulfuric acid, toward described electrolytic solution, prepare and in pond, add described appropriate dilute sulphuric acid, by heating rod, electrolytic solution is prepared to solution in pond and be heated to 45 ° of C, fully stir and by the drum machine of supporting, to described electrolytic solution, prepare drum in pond and support, make electrolytic solution prepare solution flow of solution in pond, can accelerate electrolytic solution prepare in pond the heavy metal in dry slag bag can with dilution heat of sulfuric acid rapid reaction, make in the dry slag of described mud relatively more active heavy metal be dissolved in completely and in dilute sulphuric acid, obtain the first heavy metal electrolytic solution,
Electrolytic solution is prepared in pond to the dry slag of undissolved mud to be put into whizzer and carries out separation, obtain the centrifugal dry slag of mud and the second heavy metal electrolytic solution, the centrifugal dry slag of described mud is carried out to the processing of mummification disacidify by sludge drying machine, obtain the dry slag of disacidify mud, the dry slag water ratio of described disacidify mud is below 5%, and the dry slag of described disacidify mud can be used for preparation and solidifies non-burning brick;
Described the first heavy metal electrolytic solution obtaining and the second heavy metal electrolytic solution are positioned over and in electrolyzer, form electrolytic solution, by described electrolytic solution continuous heating to 45 ° C, and continue electrolysis with the current density of 1.0ASD, generate highly purified hybrid metal electrolytic zinc-coated steel sheet; In electrolytic process, test after a while the heavy metal content in electrolytic solution, according to the continuous variation of heavy metal content in electrolytic solution, and the electric current that electrolysis is passed through also will convert use, object is to save electricity consumption, and electrolysis out can obtain high-quality hybrid metal electrolytic zinc-coated steel sheet like this.
Liquid after electricity in electrolyzer is squeezed into after electricity in liquid storage pool by pipeline with noncorrosive pump, liquid after electricity is carried out to after composition regulation, (regulate the concentration of dilution heat of sulfuric acid) and input described electrolytic solution again preparing in pond, be cycled to repeat described step b to steps d.
Embodiment 2:
Pending electroplating sludge is mixed and added in sludge drying machine with low amount copper-contained sludge, by sludge drying machine, at 950 ° of C, go down except the flammable impurity in the organism in mud and mud, obtain the dry slag of mud, and make the moisture control of the dry slag of described mud below 5%, the dry slag of such mud is convenient to subsequent disposal;
The dry slag of described mud is placed on to dry place with glass cloth bag by 10 kilograms of every bag of encapsulation pending, again the unsettled electrolytic solution that is fixed on of dry slag bag after encapsulation is prepared in the inner frame of pond, detect the heavy metal content in described dry slag bag, according to this heavy metal content, prepare appropriate dilution heat of sulfuric acid, toward described electrolytic solution, prepare and in pond, add described appropriate dilute sulphuric acid, by heating rod, electrolytic solution is prepared to solution in pond and be heated to 40 ° of C, fully stir and by the drum machine of supporting, to described electrolytic solution, prepare drum in pond and support, make electrolytic solution prepare flow of solution in pond, can accelerate electrolytic solution prepare in pond the heavy metal in dry slag bag can with dilution heat of sulfuric acid rapid reaction, make in the dry slag of described mud relatively more active heavy metal be dissolved in completely and in dilute sulphuric acid, obtain the first heavy metal electrolytic solution,
Electrolytic solution is prepared in pond to the dry slag of undissolved mud to be put into whizzer and carries out separation, obtain the centrifugal dry slag of mud and the second heavy metal electrolytic solution, the centrifugal dry slag of described mud is carried out to the processing of mummification disacidify by sludge drying machine, obtain the dry slag of disacidify mud, the dry slag water ratio of described disacidify mud is below 5%, and the dry slag of described disacidify mud can be used for preparation and solidifies non-burning brick;
Described the first heavy metal electrolytic solution obtaining and the second heavy metal electrolytic solution are positioned over and in electrolyzer, form electrolytic solution, by described electrolytic solution continuous heating to 40 ° C, and continue electrolysis with the current density of 0.5ASD, generate highly purified hybrid metal electrolytic zinc-coated steel sheet; In electrolytic process, test after a while the heavy metal content in electrolytic solution, according to the continuous variation of heavy metal content in electrolytic solution, and the electric current that electrolysis is passed through also will convert use, object is to save electricity consumption, and electrolysis out can obtain high-quality hybrid metal plate like this.
Liquid after electricity in electrolyzer is squeezed into after electricity in liquid storage pool by pipeline with noncorrosive pump, liquid after electricity is carried out to after composition regulation, (regulate the concentration of dilution heat of sulfuric acid) and input described electrolytic solution again preparing in pond, be cycled to repeat described step b to steps d.
Embodiment 3:
Pending electroplating sludge is mixed and added in sludge drying machine with low amount copper-contained sludge, by sludge drying machine, at 980 ° of C, go down except the flammable impurity in the organism in mud and mud, obtain the dry slag of mud, and make the moisture control of the dry slag of described mud below 5%, the dry slag of such mud is convenient to subsequent disposal;
The dry slag of described mud is placed on to dry place with glass cloth bag by 10 kilograms of every bag of encapsulation pending, again the unsettled electrolytic solution that is fixed on of dry slag bag after encapsulation is prepared in the inner frame of pond, detect the heavy metal content in described dry slag bag, according to this heavy metal content, prepare appropriate dilution heat of sulfuric acid, toward described electrolytic solution, prepare and in pond, add described appropriate dilute sulphuric acid, by heating rod, electrolytic solution is prepared to solution in pond and be heated to 45 ° of C, fully stir and by the drum machine of supporting, to described electrolytic solution, prepare drum in pond and support, make electrolytic solution prepare solution flow of solution in pond, can accelerate electrolytic solution prepare in pond the heavy metal in dry slag bag can with dilution heat of sulfuric acid rapid reaction, make in the dry slag of described mud relatively more active heavy metal be dissolved in completely and in dilute sulphuric acid, obtain the first heavy metal electrolytic solution,
Electrolytic solution is prepared in pond to the dry slag of undissolved mud to be put into whizzer and carries out separation, obtain the centrifugal dry slag of mud and the second heavy metal electrolytic solution, the centrifugal dry slag of described mud is carried out to the processing of mummification disacidify by sludge drying machine, obtain the dry slag of disacidify mud, the dry slag water ratio of described disacidify mud is below 5%, and the dry slag of described disacidify mud can be used for preparation and solidifies non-burning brick;
Described the first heavy metal electrolytic solution obtaining and the second heavy metal electrolytic solution are positioned over and in electrolyzer, form electrolytic solution, by described electrolytic solution continuous heating to 42 ° C, and continue electrolysis with the current density of 0.8ASD, generate highly purified hybrid metal electrolytic zinc-coated steel sheet; In electrolytic process, test after a while the heavy metal content in electrolytic solution, according to the continuous variation of heavy metal content in electrolytic solution, and the electric current that electrolysis is passed through also will convert use, object is to save electricity consumption, and electrolysis out can obtain high-quality hybrid metal plate like this.
Liquid after electricity in electrolyzer is squeezed into after electricity in liquid storage pool by pipeline with noncorrosive pump, liquid after electricity is carried out to after composition regulation, (regulate the concentration of dilution heat of sulfuric acid) and input described electrolytic solution again preparing in pond, be cycled to repeat described step b to steps d.
Than prior art, mud after electroplating sludge of the present invention and low amount copper-contained sludge integrated conduct method are not only processed can be processed into non-burning brick product, more there is the very high hybrid metal electrolytic zinc-coated steel sheet product of the purity of generation, value, far above common electroplating sludge on market and low amount copper-contained sludge treatment process, has quite significantly economic benefit and social benefit.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (5)
1. electroplating sludge and low amount copper-contained sludge integrated conduct method, is characterized in that, said method comprising the steps of:
Step a: pending electroplating sludge is mixed and added in sludge drying machine with low amount copper-contained sludge, organism by sludge drying machine in 950 ~ 1000 ° of C removal mud and the flammable impurity in mud, obtain the dry slag of mud, and make the moisture control of the dry slag of described mud below 5%;
Step b: the dry slag of described mud is prepared to pond with putting into electrolytic solution after the encapsulation of glass cloth bag, toward described electrolytic solution, prepare pond and add appropriate dilute sulphuric acid, fully stir, heavy metal in the dry slag of described mud is dissolved in completely and in dilute sulphuric acid, obtains the first heavy metal electrolytic solution;
Step c: electrolytic solution is prepared in pond to the dry slag of undissolved mud and put into whizzer and carry out separation, obtain the centrifugal dry slag of mud and the second heavy metal electrolytic solution;
Steps d: described the first heavy metal electrolytic solution obtaining and the second heavy metal electrolytic solution are positioned over and form electrolytic solution in electrolyzer, by described electrolytic solution continuous heating to 40 ~ 45 ° C, and continue electrolysis with the current density of 0.5 ~ 1.0ASD, generate highly purified hybrid metal electrolytic zinc-coated steel sheet.
2. electroplating sludge according to claim 1 and low amount copper-contained sludge integrated conduct method, is characterized in that, described step b specifically comprises:
The dry slag of described mud is packaged into dry slag bag the unsettled electrolytic solution that is fixed on glass cloth bag to be prepared in the inner frame of pond, detect the heavy metal content in described dry slag bag, according to this heavy metal content, prepare appropriate dilution heat of sulfuric acid, toward described electrolytic solution, prepare and in pond, add described appropriate dilute sulphuric acid, by heating rod, electrolytic solution is prepared to solution in pond and be heated to 40 ~ 45 ° of C, fully stir and also by the drum machine of supporting, to described electrolytic solution, prepare in pond bulging fosterly, heavy metal in the dry slag of described mud is dissolved in completely and in dilute sulphuric acid, obtains the first heavy metal electrolytic solution.
3. electroplating sludge according to claim 1 and low amount copper-contained sludge integrated conduct method, it is characterized in that, described step c also comprises: the centrifugal dry slag of described mud is carried out to the processing of mummification disacidify by sludge drying machine, and the dry slag of described disacidify mud can be used for preparation and solidifies non-burning brick.
4. electroplating sludge according to claim 3 and low amount copper-contained sludge integrated conduct method, is characterized in that, the water ratio of the dry slag of described disacidify mud is below 5%.
5. according to the electroplating sludge described in claim 1-4 any one and low amount copper-contained sludge integrated conduct method, it is characterized in that, after described steps d, also comprise: liquid after the electricity after electrolysis is added into described electrolytic solution and prepares in pond, be cycled to repeat described step b to steps d.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104789781A (en) * | 2015-03-27 | 2015-07-22 | 昆山市益民环保技术开发有限公司 | Processing method for comprehensive resource utilization of electroplating sludge and waste activated carbon |
| CN106978609A (en) * | 2017-04-26 | 2017-07-25 | 昆山市益民环保技术开发有限公司 | The recovery of copper and Comprehensive utilization method in copper-contained sludge |
| CN107140808A (en) * | 2017-04-26 | 2017-09-08 | 昆山市益民环保技术开发有限公司 | The recovery of nickel and Comprehensive utilization method in nickel-containing sludge |
| CN108383485A (en) * | 2018-04-19 | 2018-08-10 | 宁波纯恒固废科技有限公司 | Non-autoclaved and unburned brick of a kind of electroplating sludge compacting and preparation method thereof |
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| CN102173547A (en) * | 2011-03-29 | 2011-09-07 | 苏州市环境工程有限责任公司 | Resource recycling process for nickel-containing sludge in electroplating enterprises |
| CN102994762A (en) * | 2012-12-21 | 2013-03-27 | 嘉兴科菲冶金科技股份有限公司 | Industrial method for selectively recycling copper and nickel from copper-nickel mud |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104789781A (en) * | 2015-03-27 | 2015-07-22 | 昆山市益民环保技术开发有限公司 | Processing method for comprehensive resource utilization of electroplating sludge and waste activated carbon |
| CN106978609A (en) * | 2017-04-26 | 2017-07-25 | 昆山市益民环保技术开发有限公司 | The recovery of copper and Comprehensive utilization method in copper-contained sludge |
| CN107140808A (en) * | 2017-04-26 | 2017-09-08 | 昆山市益民环保技术开发有限公司 | The recovery of nickel and Comprehensive utilization method in nickel-containing sludge |
| CN108383485A (en) * | 2018-04-19 | 2018-08-10 | 宁波纯恒固废科技有限公司 | Non-autoclaved and unburned brick of a kind of electroplating sludge compacting and preparation method thereof |
| CN108383485B (en) * | 2018-04-19 | 2021-03-23 | 宁波纯力固废科技有限责任公司 | Non-steamed baking-free brick pressed by electroplating sludge and preparation method thereof |
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