CN201587966U - Device for recycling high-purity copper oxide from copper bearing sludge resources - Google Patents
Device for recycling high-purity copper oxide from copper bearing sludge resources Download PDFInfo
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- CN201587966U CN201587966U CN2009201630794U CN200920163079U CN201587966U CN 201587966 U CN201587966 U CN 201587966U CN 2009201630794 U CN2009201630794 U CN 2009201630794U CN 200920163079 U CN200920163079 U CN 200920163079U CN 201587966 U CN201587966 U CN 201587966U
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P10/20—Recycling
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Abstract
The utility model provides a device for recycling high-purity copper oxide from copper bearing sludge resources, which consists of a sludge temporary storage tank, a homogenizing tank, a pickling oxidation reaction tank, a solid and liquid separator, an ammonia leaching reaction tank, a copper carbonate reaction tank, a residue homogenizing repeating tank, an alkali liquid temporary storage tank, a washing tank, a roaster and a computer monitoring recorder. Copper content and impurity of high-purity copper fine powder recycled from copper bearing sludge which is recycled as a resource both meet requirements on commercial copper oxide, can be used as raw materials for after copper electrolysis, ammonia water can be recycled by aid of an ammonia evaporation process, ammonia leaching agent additive amount is reduced, and filtered alkali liquid can be recycled and led into a waste water system, treated together with waste water and used as a neutralizer. Compared with other treatment methods, the device has the advantages of low operation cost and high recovery economic benefit.
Description
Technical field
The utility model relates to a kind of device of copper mud goods, materials and equipments recovery high-purity mangesium oxide copper, provide goods, materials and equipments recovery purification process at cuprics that processing procedure produces such as printed circuit board (PCB) industry, surface treatment industry, wire rod processing industries for main heavy metal sewage sludge especially, effectively copper-contained sludge is reclaimed and make high-purity mangesium oxide copper reconstituted product, meet commercial oxidation copper products specification, as the former material of electrolytic copper in the processing procedure, replace the former material of copper carbonate, significantly reduce harmful sludge treatment expense, and create the high economic worth that reclaims.
Background technology
Because copper-contained sludge belongs to the limited metals resources of exhaustion of artificial mineral, can't regenerate, and wherein copper content can be exploited 0.5% cut-off grade apparently higher than copper mine, be the metals resources that is worth reclaiming.Copper-contained sludge resource utilization way of recycling is divided into wet type and metallurgical two classes of dry type, wet method have acid molten, alkali is molten with after the stripping of purpose metal, purifying reclaims valuable metal, as with copper-contained sludge after pure aftertreatment flow processs such as acid dipping and solvent extraction, copper-bath is made in recovery, but running cost is higher relatively low with the reconstituted product unit price, and dipping back residue can't meet the TCLP standard, and filter dehydration also causes the dealer to perplex.Compared to wet processing, reclaim in the at present domestic mostly collection, utilize dry type to smelt mode Treatment of Copper heavy metal sewage sludge, use big calorimetric, electric energy with the moisture evaporation in the mud, reach reducing sludge volume, decrement, use and improve valuable metal content, transfer other country's copper smelting plant after treatment to and carry out the copper recovery, cause that the manipulation expense is higher relatively, the power consumption of deriving can't be stayed domestic recycle with problem such as flue dust environmental protection and copper metals resources, very unfortunate.Estimate according to investigation and statistics, the circuit card industry copper-contained sludge of domestic output annual about 31,000 ton, Copper Foil factory mud generating capacity annual about 21,000 ton, the amount of estimating of electroplating sludge is about 94,000 tons every year, therefore the circuit card industry is about 146,000 tons with the annual mud amount of estimating of electroplating metal finishing industry such as industry.Generally speaking, the synthetic method commonly used of preparation cupric oxide powder is (1) hydrothermal method (2) chemical precipitation method (3) sol-gel method and (4) microemulsion method.Because the cupric oxide fine powder can be as broad-spectrum multifunctional inorganic material, the tool uniqueness electrically, characteristics such as magnetic, catalytic active substance, be widely used in key areas such as magnetic stored material, gas sensing device, solar cell, support of the catalyst and electrode active material.This goods, materials and equipmentsization processing intent, utilize acid dipping and selectivity ammonia dipping two-stage to reclaim and make the reconstituted product of highly purified cupric oxide fine powder copper-contained sludge, and meet commercial copper carbonate product specification, as the former material of electrolytic copper, replace the former material of cupric oxide, create the high economic worth that reclaims.
Summary of the invention
Goal of the invention of the present utility model, device that provides copper mud goods, materials and equipments recovery high-purity mangesium oxide copper mainly is provided for it, and interpolation sulfuric acid and strong oxidizer are removed processing procedure and are produced high grease organism in the treating processes, utilize selectivity ammonia impregnating process, reclaim purifying basic carbonate copper solutions, adopt the circulation dipping to improve copper recovery ammonia dipping back residue in the process, improve traditional ammonia dipping copper recovery on the low side, and utilize the ammonia still process program, and reclaim ammoniacal liquor, reduce ammonia dipping additive amount of medicament.Yet the alkali lye that generates copper carbonate imports waste water system merges processing, significantly lowers the alkali addition, utilizes dechlorination water repetitiousness water-washing method to remove impurities such as chlorine at last again, and product meets cupric oxide commerical prod specification.This goods, materials and equipmentsization treatment technology has low process cost and bigger recovery economic benefit with respect to other wet type recycling modes.
The technical solution of the utility model is: a kind of device of copper mud goods, materials and equipments recovery high-purity mangesium oxide copper includes:
One mud temporary tank is for depositing the copper-contained sludge cake;
One mixes well groove, mud is added hot water puddle and size mixing, and forms even slurry;
One acid dipping oxidizing reaction groove, with mix well groove and be connected, be that slurry adds medicaments such as an amount of sulfuric acid and hydrogen peroxide, keep reactive tank pH value less than 3.0, continue heating, aeration and stirring in the process, make that the stripping of heavy metal hydroxide dipping is metal ion attitude and oil slick layer in the mud;
One solid-liquid separating machine is connected with acid dipping oxidizing reaction groove, and the cupric oil slick solution of acid dipping oxidizing reaction groove is carried out solid-liquid separation, removes oil slick, forms high density copper-containing solution and waste oil residue, and the high density copper-containing solution directly imports ammonia dipping reactive tank;
One ammonia dipping reactive tank, be connected with solid-liquid separating machine, the high density copper-containing solution adds medicaments such as ammoniacal liquor and volatile salt in right amount, keep in the reactive tank pH value of solution value between 9.0～10.0, continue heated and stirred in the dipping purge process, accelerated reaction is carried out, and forms the wrong solion (Cu (NH of mazarine cuprammonium after reaction is finished
3)
4 2+) complexes) and residue;
One copper carbonate reactive tank is connected with solid-liquid separating machine, with the wrong solion (Cu (NH of cuprammonium
3)
4 2+) add medicament such as liquid caustic soda, adjusting the pH value of solution value is 11.0, reaction forms the basic carbonate copper solutions gradually;
One alkali lye temporary tank is for depositing from the high pH value filtrate after the filtration of copper carbonate reactive tank;
One rinse bath behind the repetitiousness washing filtering, reduces in the solution impurities such as chlorinity with the copper carbonate solid product;
One stoving oven: be that the copper carbonate product after the washing is carried out being burnt and time control, change, form the high-purity mangesium oxide copper fine powder via crystallization phases;
One computer monitoring registering instrument: be to carry out reaction parameter setting, demonstration, monitoring and record at mixing well groove, acid dipping oxidizing reaction groove, ammonia dipping reactive tank, copper carbonate reactive tank and stoving oven.
Above-mentioned mud temporary tank and alkali lye temporary tank are the storage tanks of acid and alkali-resistance.
Above-mentionedly mix well groove, residue mixes well the relaying groove and rinse bath is all acid and alkali-resistance bucket groove, install to the adjustable speed stirrer to be constituted.
Above-mentioned acid dipping oxidizing reaction groove, ammonia dipping reactive tank and copper carbonate reactive tank are all the acid and alkali-resistance reactive tank, and device comprises an adjustable speed stirrer, an adjustable speed air aeration machine, a heating controller.
Above-mentioned solid-liquid separating machine can be band filter formula, centrifugal, screw, circle trunk vacuum filtration formula or plate and frame(type)filter press or vacuum filter or whizzer.
Above-mentioned computer monitoring registering instrument is a full-automatic computer line monitor, carry out reaction parameter at mixing well groove, acid dipping oxidizing reaction groove, ammonia dipping reactive tank, copper carbonate reactive tank and stoving oven, comprise setting, demonstration, monitoring, caution and the automatic record of parameters such as temperature of reaction, reaction times, pH and ORP.
Description of drawings
Fig. 1 is a device synoptic diagram of the present utility model;
Attached figure labeling description:
10: mud temporary tank 20: mix well groove
21: residue is mixed well relaying groove 30: acid dipping oxidizing reaction groove
40: solid-liquid separating machine (1) 41: solid-liquid separating machine (2)
42: solid-liquid separating machine (3) 43: solid-liquid separating machine (4)
50: ammonia dipping reactive tank 60: copper carbonate reactive tank
70: alkali lye temporary tank 80: rinse bath
90: stoving oven 100: the computer monitoring registering instrument
S: solid phase L: liquid phase M: mixed phase W: RCA
Embodiment
About the utility model for reaching above-mentioned application target and effect, the technique means that is adopted is enumerated preferable feasible embodiment now, and cooperates shown in the diagram, details are as follows:
At first, as shown in Figure 1: the device of the copper mud goods, materials and equipments recovery high-purity mangesium oxide copper of present embodiment mainly is by mud temporary tank 10, mix well groove 20, residue is mixed well relaying groove 21, acid dipping oxidizing reaction groove 30, solid-liquid separating machine (1) 40, solid-liquid separating machine (2) 41, solid-liquid separating machine (3) 42, solid-liquid separating machine (4) 43, ammonia dipping reactive tank 50, copper carbonate reactive tank 60, alkali lye temporary tank 70, rinse bath 80, stoving oven 90 and computer monitoring registering instrument 100 and formed.Wherein the mud temporary tank 10, usefulness for temporary copper-contained sludge, mixing well groove 20 is connected with mud temporary tank 10, importing mud and hot water are puddled and are sized mixing, cell body comprises a gang of Pu, a control valve, a under meter, an agitator, a well heater and a temperature controller, lie in utilize control valve and under meter to add quantitative hot water in the groove (according to hot water: the optimum operation ratio of wet basis copper-contained sludge 5: 1) operating and carrying out temperature of reaction is the 80 degree Celsius programs of sizing mixing, and mud is formed even slurry.Acid dipping oxidizing reaction groove 30 with mix well groove 20 and be connected, import slurry and add medicaments such as suitable sulfuric acid and hydrogen peroxide, cell body comprises a gang of Pu, a control valve, a under meter, a pH meter, ORP meter, an aeration conduit, an agitator, a well heater and a temperature controller, lie in and utilize control valve control slurry flow in the groove and add the most suitable pH value and the ORP potential value of medicament adjustment, and to carry out temperature of reaction be 80 degree acid dipping oxidation programs Celsius, is metal ion attitude and oil slick layer with heavy metal hydroxide dipping stripping in the mud.Solid-liquid separating machine (1) 40 is connected with acid dipping oxidizing reaction groove 30, and acid dipping oxidizing reaction after-filtration is removed oil slick, and the copper-containing solution of formation liquid phase reaches the waste oil residue with solid phase.Ammonia dipping reactive tank 50 is connected with solid-liquid separating machine (1) 40, import copper-containing solution and add medicaments such as suitable ammoniacal liquor and volatile salt, cell body comprises a gang of Pu, a control valve, a under meter, a pH meter, ORP meter, an aeration conduit, an agitator, an ammonia distiller, a condensation recovery tube, a well heater and a temperature controller, lie in and utilize the control valve dominant discharge in the groove and add the most suitable pH value and the ORP potential value of medicament adjustment, and to carry out temperature of reaction be 80 degree ammonia impregnating processs Celsius, will form mazarine cuprammonium mistake solion (Cu (NH
3)
4 2+) complexes), and utilize the ammonia still process program, and reclaim ammoniacal liquor, reduce ammonia dipping additive amount of medicament.Solid-liquid separating machine (2) 41 is connected with ammonia dipping reactive tank 50, with wrong solion of filtering separation ammonification and solid phase residue.Residue is mixed well relaying groove 21 and is connected with solid-liquid separating machine (2) 41, concentrates ammonia dipping back residue, takes circulation dipping purifying mode, imports and mixes well groove 20 repeated impregnations, uses the raising copper recovery, and final residue carries out harmless treatment again.Copper carbonate reactive tank 60 is connected with solid-liquid separating machine (2) 41, to add suitable liquid caustic soda medicament in the wrong solion of the cuprammonium behind the ammonia dipping, cell body comprises a gang of Pu, a control valve, a under meter, a pH meter, ORP meter, an aeration conduit, an agitator, a well heater and a temperature controller, lie in and utilize the control valve dominant discharge in the groove and adjust the most suitable pH value and ORP potential value, progressively form the basic carbonate copper solutions after waiting to add alkali reaction.Solid-liquid separating machine (3) 42 is connected with copper carbonate reactive tank 60, with filtering separation ventilation breather and alkali lye.Alkali lye temporary tank 70 is connected with solid-liquid separating machine (3) 42, and temporary high pH value alkali lye, and import waste water system and merge and handle significantly lowers in the liquid caustic soda addition with medicament.Rinse bath 80 is connected with solid-liquid separating machine (3) 42, and the ventilation breather throw out after solid-liquid separating machine (3) 42 is separated is removed impurities such as chlorine via the multiple water-washing step, imports waste water system and merges processing.Solid-liquid separating machine (4) 43 is connected with rinse bath 80, the chloride impurity that waits of filtering separation.Stoving oven 90 is connected with solid-liquid separating machine (4) 43, and with 600 ℃ of the ventilation breather product utilization maturing temperatures after filtering, 3 hours reaction times was carried out the copper carbonate crystal transition, formed the high-purity mangesium oxide copper fine powder.Computer monitoring registering instrument 100 is connected with stoving oven 90, carries out reaction parameter (comprising temperature of reaction, reaction times, pH value and ORP etc.) setting, demonstration, monitoring, caution and record at mixing well groove, acid dipping oxidizing reaction groove, ammonia dipping reactive tank, copper carbonate reactive tank and stoving oven.In addition mud temporary tank 10, to mix well groove 20, acid dipping oxidizing reaction groove 30, ammonia dipping reactive tank 50, copper carbonate reactive tank 60, alkali lye temporary tank 70 all be to utilize the shock-resistant cell body made from the acid and alkali-resistance material with rinse bath 80.
Via above explanation as can be known, this creation has following advantage really:
1. this device utilizes acid dip oxidation program, with metal hydroxides molten be metal ion, and add strong oxidizer and remove high grease organic matter.
2. this device utilizes selective ammonia impregnating process, reclaims the purifying basic copper carbonate.
3. this device utilizes the circulation dipping to improve copper recovery in the residue, improves traditional ammonia dipping copper recovery on the low side.
4. this device utilizes the ammonia still process program, reclaims ammoniacal liquor, reduces ammonia dipping additive amount of medicament.
5. this device alkali lye of generating copper carbonate imports waste water system and merges and process, in significantly lowering and medicament-liquid caustic soda addition.
6. the impurity such as this device repetitiousness water-washing method dechlorination, product meets the cupric oxide commercial specification.
7. this device has low cost of investment, reduction process cost, high economic recovery benefit with respect to other processing modes. Except reducing the environmental pollution of copper mud, more and then promote that cupric is the goods, materials and equipments of main heavy metal sewage sludge, and slow down the speed that natural resources are exhausted, so be one novel and have a device of the copper mud goods, materials and equipments recovery high-purity mangesium oxide copper of practicality.
8. the processing instrument size of this device can be used according to different factory processes scale adjustment, therefore meet the at present demand of the industry other places reason present situation of domestic relevant copper mud generating capacity, needs on the collocation actual treatment have industry utilizability and generalization.
Claims (6)
1. the device of a copper mud goods, materials and equipments recovery high-purity mangesium oxide copper is characterized in that including:
A kind of mud temporary tank;
A kind of groove of mixing well;
One acid dipping oxidizing reaction groove and is mixed well groove and is connected;
One solid-liquid separating machine is connected with acid dipping oxidizing reaction groove;
One ammonia dipping reactive tank is connected with solid-liquid separating machine;
One copper carbonate reactive tank is connected with solid-liquid separating machine;
One alkali lye temporary tank;
One rinse bath;
One stoving oven;
One computer monitoring registering instrument.
2. the device of copper mud goods, materials and equipments recovery high-purity mangesium oxide copper as claimed in claim 1 is characterized in that wherein mud temporary tank and alkali lye temporary tank are the storage tanks of acid and alkali-resistance.
3. the device of copper mud goods, materials and equipments recovery high-purity mangesium oxide copper as claimed in claim 1 is characterized in that wherein mixing well groove, residue mixes well the relaying groove and rinse bath is all acid and alkali-resistance bucket groove, installs to the adjustable speed stirrer to be constituted.
4. the device of copper mud goods, materials and equipments recovery high-purity mangesium oxide copper as claimed in claim 1, it is characterized in that wherein acid dipping oxidizing reaction groove, ammonia dipping reactive tank and copper carbonate reactive tank are all the acid and alkali-resistance reactive tank, device comprises an adjustable speed stirrer, an adjustable speed air aeration machine, a heating controller.
5. the device of copper mud goods, materials and equipments recovery high-purity mangesium oxide copper as claimed in claim 1 is characterized in that described solid-liquid separating machine can be band filter formula, centrifugal, screw, circle trunk vacuum filtration formula or plate and frame(type)filter press or vacuum filter or whizzer.
6. the device of copper mud goods, materials and equipments recovery high-purity mangesium oxide copper as claimed in claim 1 is characterized in that described computer monitoring registering instrument is a full-automatic computer line monitor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009201630794U CN201587966U (en) | 2009-08-12 | 2009-08-12 | Device for recycling high-purity copper oxide from copper bearing sludge resources |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009201630794U CN201587966U (en) | 2009-08-12 | 2009-08-12 | Device for recycling high-purity copper oxide from copper bearing sludge resources |
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| Publication Number | Publication Date |
|---|---|
| CN201587966U true CN201587966U (en) | 2010-09-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009201630794U Expired - Fee Related CN201587966U (en) | 2009-08-12 | 2009-08-12 | Device for recycling high-purity copper oxide from copper bearing sludge resources |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102345014A (en) * | 2011-07-01 | 2012-02-08 | 冯若愚 | Method for preparing elementary copper, copper hydroxide and sodium chloride through dye waste residues |
| CN102815779A (en) * | 2011-06-08 | 2012-12-12 | 株式会社东芝 | Copper recovery apparatus |
| WO2013096070A1 (en) * | 2011-12-20 | 2013-06-27 | Freeport-Mcmoran Corporation | Systems and methods for metal recovery |
| CN104891551A (en) * | 2014-03-04 | 2015-09-09 | 金居开发铜箔股份有限公司 | Copper oxide making method and copper oxide making equipment |
-
2009
- 2009-08-12 CN CN2009201630794U patent/CN201587966U/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102815779A (en) * | 2011-06-08 | 2012-12-12 | 株式会社东芝 | Copper recovery apparatus |
| CN102815779B (en) * | 2011-06-08 | 2014-06-11 | 株式会社东芝 | Copper recovery apparatus |
| US8986541B2 (en) | 2011-06-08 | 2015-03-24 | Kabushiki Kaisha Toshiba | Copper recovery apparatus |
| US9701553B2 (en) | 2011-06-08 | 2017-07-11 | Kabushiki Kaisha Toshiba | Copper recovery apparatus |
| CN102345014A (en) * | 2011-07-01 | 2012-02-08 | 冯若愚 | Method for preparing elementary copper, copper hydroxide and sodium chloride through dye waste residues |
| WO2013096070A1 (en) * | 2011-12-20 | 2013-06-27 | Freeport-Mcmoran Corporation | Systems and methods for metal recovery |
| CN104891551A (en) * | 2014-03-04 | 2015-09-09 | 金居开发铜箔股份有限公司 | Copper oxide making method and copper oxide making equipment |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100922 Termination date: 20140812 |
|
| EXPY | Termination of patent right or utility model |