CN106929686A - A kind of method that copper in ferric trichloride etching waste liquor is reclaimed in utilization metal sludge collaboration - Google Patents
A kind of method that copper in ferric trichloride etching waste liquor is reclaimed in utilization metal sludge collaboration Download PDFInfo
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- CN106929686A CN106929686A CN201710229033.7A CN201710229033A CN106929686A CN 106929686 A CN106929686 A CN 106929686A CN 201710229033 A CN201710229033 A CN 201710229033A CN 106929686 A CN106929686 A CN 106929686A
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- copper
- ferric trichloride
- waste liquor
- sludge
- etching waste
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
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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
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The present invention relates to the method that copper in ferric trichloride etching waste liquor is reclaimed in a kind of collaboration of utilization metal sludge, will size mixing squeeze water and piece alkali of metal sludge certain density alkaline adjusting slurry is made into size-mixing tank, to the metal sludge that fixed proportion is added in the alkaline adjusting slurry, open stirring, it is well mixed metal sludge adjusting slurry, to ferric trichloride etching waste liquor is added in size-mixing tank, the pH value of adjusting slurry is adjusted, it is ensured that the copper ion in ferric trichloride etching waste liquor is precipitated completely.Mixing sludge in size-mixing tank is pumped to diaphragm pressing machine press dewatering, squeezing water section is back to the alkaline adjusting slurry of configuration, and other can directly carry out biochemical treatment, and cost for wastewater treatment is low, the squeezing sludge of generation is further dried rear briquetting and sends into smelting furnace smelting, obtains product copper bullion.The advantage of the invention is simple technological process, can make full use of existing heavy metal sewage sludge dehydration smelting equipment, and raw material collaboration utilization rate is high, with preferable Social benefit and economic benefit.
Description
Technical field
The present invention relates to the method that copper in ferric trichloride etching waste liquor is reclaimed in a kind of collaboration of utilization metal sludge, belong to trichlorine
Change iron etching waste liquor copper resource comprehensive reutilization and environmental technology field.
Technical background
Liquor ferri trichloridi is widely used in copper in printed circuit board industry, even as a kind of extremely strong lewis acid
The etching of stainless steel, the copper ion containing about 55~85g/L in the waste liquid after etching,、Content it is also higher.Cupric
Ferric trichloride waste liquid belongs to hazardous waste, if not using effective recovering meanses or dealing with improperly, will certainly cause
The waste and environmental pollution of valency metals resources.Therefore, copper resource is carried out to cupric ferric trichloride waste liquid to recycle with certain
Economic benefit and environmental benefit.
At present, the handling process industrially to ferric trichloride etching waste liquor mainly has iron replacement method, direct electrolysis method.Specially
Sharp CN102912352A is disclosed " a kind of acid copper waste etching solution recycling method ", it is characterised in that the lower oxytropism of stirring
Reduced iron is added in etching waste liquor, copper sponge is separated out, the moisture content of wherein sponge copper products reaches 50%.Patent
CN101462803A is disclosed " a kind of containing copper chloride, ferric trichloride etching waste liquor regeneration recovery method ", it is characterised in that use iron
Powder reduces bivalent cupric ion and ferric ion, isolates copper-clad Iron speciation sediment.Common using iron replacement method lacks
Point is that iron powder adds must be excessive, and otherwise etching solution copper ion is difficult that displacement is complete, and the purity of the product copper sponge for obtaining is often
It is not high, containing more iron simple substance, have a negative impact to follow-up separation.Patent CN101353795A is disclosed " will be printed
Circuit board acidic etching waste liquor puies forward copper and the method for preparing poly-ferric chloride ", it is characterised in that printed circuit board acidic is etched
Waste liquid Direct Electrolysis, reclaim the copper powder that electrolysis is separated out, and to reduced iron is added in the mixed liquor after electrolysis, replace the ion of mixed liquor
Copper, reclaims the copper sponge that displacement is separated out.Electrolysis copper extraction method mainly needs to consider the chlorine emission problem that anode is separated out, is electrolysed past
It is unsatisfactory toward the etching solution effect to low concentration, in electrolytic process, put forward copper efficiency and constantly decline, while elemental copper has being weighed
The possibility of new oxidation dissolution, therefore carry the electrolyte after copper and still need using the further copper removal of other method, additionally, electrolysis process is also
Face the low deficiency of electrolysis high cost, device disposal ability.
The content of the invention
The invention provides the method that copper in ferric trichloride etching waste liquor is reclaimed in a kind of collaboration of utilization metal sludge, in technique
The methods such as the displacement, the electrolysis that are generally used in the treatment of traditional ferric trichloride etching waste liquor are jumped out in design, this technique not only reality
Effective recovery of copper resource is showed, has also solved the waste water handling problem of surplus solution, be a kind of technical scheme of Environmental Safety.
The technical solution adopted by the present invention is：With metal sludge as carrier, supplemented by piece alkali, cupric ferric trichloride etching waste liquor
Raw material is helped, neutralization precipitation, purification suction-operated using metal sludge alkalescence adjusting slurry to ferric trichloride etching waste liquor, by trichlorine
Change the complete precipitation adsorption of copper ion in iron etching waste liquor in sludge, it is molten by further reinforcing dehydration, heated-air drying, briquetting
Refining, finally gives copper bullion, and the method is comprised the following steps：（1）To squeezing recycle-water is injected in size-mixing tank, stirring is opened, thrown
Enter piece alkali and dissolve complete, be configured to alkaline adjusting slurry；（2）The metal sludge of moisture content about 80%~85% is added to and is sized mixing
Pond, stir about 40 minutes, it is ensured that metal sludge adjusting slurry is well mixed；（3）Etched to ferric trichloride is slowly added in size-mixing tank
Waste liquid, adjusts the pH value of adjusting slurry, until the copper in ferric trichloride etching waste liquor, in the complete precipitation adsorption of iron ion to sludge,
Stop stirring, sludge in size-mixing tank is sent into diaphragm pressing machine with screw pump is dehydrated；（4）The metal sludge warp of strong force squeezing dehydration
Further removing moisture in belt feeding rotary drying kiln, dried sludge is made pelletizing and is transported to smelting furnace and carries out high temperature melting
Refining, casting obtains product copper bullion.
Further, in above-mentioned technical proposal, described metal sludge is mainly derived from Surface Processing Industry and wiring board
The copper ion that the copper-containing wastewater produced in the operations such as manufacturing etching, brushing, electroless copper plating and electro-coppering is produced after treatment
Enrichment sludge.
Further, in above-mentioned technical proposal, copper content is general in 55~85g/ in described ferric trichloride etching waste liquor
L, density is generally 1.32~1.45g/cm-3, Baume degrees is generally 30~45 ° of B é.
Further, in above-mentioned technical proposal, described metal sludge, squeezing recycle-water, ferric trichloride etching waste liquor, piece
The dosage of alkali meets following relation, metal sludge：Squeezing recycle-water：Ferric trichloride etching waste liquor：Piece alkali dosage=1:3:
0.1675:0.0318（Mass ratio）.
Further, in above-mentioned technical proposal, described adjusting slurry final ph is 6.5.
Further, in above-mentioned technical proposal, through the dry copper-contained sludge moisture content 10%~15% of hot-blast stove, high melt
Temperature be 1300~1400 DEG C.
The present invention compared with prior art, has the following advantages that：
（1）The method that the present invention does not use iron replacement, does not have inflammable and explosive hydrogen to produce, the product of the copper sponge that displacement method is obtained
Position is not general high（Copper content is usually no more than 70%）, the copper content of the copper bullion obtained by melting is generally greater than 80%, this work
The copper products content that skill is obtained improves at least 10%.
（2）The method that the present invention does not use Direct Electrolysis, does not have toxic gas chlorine to produce, and copper content is not in pressing filtrate
To 1mg/L, copper resource is sufficiently recycled, and heavy copper is settled at one go, it is not necessary to extra multiple copper removal operation.
（3）The materials such as raw material molysite, by-product iron hydroxide used in the present invention are in itself to the impurity in metal sludge
Certain flocculation sediment effect can be played, while the porous of metal sludge imparts the ability of sludge absorption iron, copper ion, gold
Category sludge, ferric trichloride etching waste liquor collaboration Treatment Effects are notable.
（4）Present invention process safety and environmental protection, flow is simple, continuously can realize on a large scale to ferric trichloride etching waste liquor
Comprehensive utilization is processed, and is adapted to industrialization.
Brief description of the drawings
Fig. 1 is that the method flow that copper in ferric trichloride etching waste liquor is reclaimed in a kind of utilization metal sludge collaboration of the invention is illustrated
Figure.
Specific embodiment
Process of the invention is described in further detail below with reference to specific embodiment of the invention.
（1）To squeezing recycle-water 15.8t is injected in size-mixing tank, stirring is opened, put into piece alkali 159kg and dissolve complete, matched somebody with somebody
It is set to alkaline adjusting slurry；
（2）The metal sludge 5t of moisture content about 84% is added to size-mixing tank, stir about 40 minutes, it is ensured that metal sludge adjusting slurry
It is well mixed；
（3）To ferric trichloride etching waste liquor 837.5kg is slowly added in size-mixing tank, the pH value of adjusting slurry to 6.5, Zhi Daosan is adjusted
The complete precipitation adsorption of copper, iron ion in iron chloride etching waste liquor in sludge, with screw pump by sludge in size-mixing tank send into every
Mould crusher is dehydrated, and following table is material major parameter situation of change after metal sludge, ferric trichloride etching waste liquor collaboration before processing.
As can be seen from the above table, after ferric trichloride etching waste liquor cooperates with treatment with metal sludge, the squeezing recycle-water of gained
Middle copper, iron ion content are extremely low, and compared to ferric trichloride etching waste liquor, the rate of recovery of copper reaches 99.6%.
（4）The metal sludge of strong force squeezing dehydration in belt feeding rotary drying kiln through further removing moisture（Sludge contains
Water rate 11.5%）, dried sludge is made pelletizing and is transported to smelting furnace and carry out high melt（1350 DEG C of smelting temperature）, cast
To product copper bullion, copper content about 85%.
The above, the only present invention preferably specific embodiment, but protection scope of the present invention is not limited thereto,
Any one skilled in the art in the technical scope of present disclosure, technology according to the present invention scheme and its
Design is subject to equivalent or change, should all be included within the scope of the present invention.
Claims (6)
1. a kind of method that copper in ferric trichloride etching waste liquor is reclaimed in utilization metal sludge collaboration, it is characterised in that including following
Step：
（1）To squeezing recycle-water is injected in size-mixing tank, stirring is opened, put into piece alkali and dissolve complete, be configured to alkaline adjusting slurry；
（2）The metal sludge of moisture content about 80%~85% is added to size-mixing tank, stir about 40 minutes, it is ensured that metal sludge is sized mixing
Liquid is well mixed；
（3）To ferric trichloride etching waste liquor is slowly added in size-mixing tank, the pH value of adjusting slurry is adjusted, until ferric trichloride etching is useless
Sludge in size-mixing tank is sent into diaphragm pressing machine and is dehydrated by the complete precipitation adsorption of copper, iron ion in liquid in sludge with screw pump；
（4）The metal sludge of strong force squeezing dehydration in belt feeding rotary drying kiln through further removing moisture, dried dirt
Mud is made pelletizing and is transported to smelting furnace and carries out high melt casting, obtains product copper bullion.
2. the method that copper in ferric trichloride etching waste liquor is reclaimed in a kind of utilization metal sludge collaboration according to claim 1,
Characterized in that, described metal sludge is mainly derived from Surface Processing Industry and the etching of wiring board manufacturing, brushing, chemistry
The copper ion enrichment sludge that the copper-containing wastewater produced in the operations such as heavy copper and electro-coppering is produced after treatment.
3. the method that copper in ferric trichloride etching waste liquor is reclaimed in a kind of utilization metal sludge collaboration according to claim 1,
Characterized in that, copper content is general in 55~85g/L in described ferric trichloride etching waste liquor, density is generally 1.32~
1.45g/cm-3, Baume degrees is generally 30~45 ° of B é.
4. the method that copper in ferric trichloride etching waste liquor is reclaimed in a kind of utilization metal sludge collaboration according to claim 1,
Characterized in that, described metal sludge, squeezing recycle-water, ferric trichloride etching waste liquor, the dosage of piece alkali are met with ShiShimonoseki
System, metal sludge：Squeezing recycle-water：Ferric trichloride etching waste liquor：The mass ratio of piece alkali dosage is 1:3:0.1675:
0.0318。
5. the method that copper in ferric trichloride etching waste liquor is reclaimed in a kind of utilization metal sludge collaboration according to claim 1,
Characterized in that, described adjusting slurry final ph is 6.5.
6. the method that copper in ferric trichloride etching waste liquor is reclaimed in a kind of utilization metal sludge collaboration according to claim 1,
Characterized in that, through the dry copper-contained sludge moisture content 10%~15% of rotary drying kiln, high melt temperature is 1300~1400
℃。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710229033.7A CN106929686B (en) | 2017-04-10 | 2017-04-10 | Method for cooperatively recovering copper in ferric trichloride etching waste liquid by utilizing metal sludge |
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| CN201710229033.7A CN106929686B (en) | 2017-04-10 | 2017-04-10 | Method for cooperatively recovering copper in ferric trichloride etching waste liquid by utilizing metal sludge |
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| CN106929686A true CN106929686A (en) | 2017-07-07 |
| CN106929686B CN106929686B (en) | 2020-06-23 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107828974A (en) * | 2017-10-23 | 2018-03-23 | 广东绿晟环保股份有限公司 | A kind of waste printed circuit board combined treatment process |
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| CN103422119A (en) * | 2013-07-19 | 2013-12-04 | 紫金矿业集团股份有限公司 | Method for producing tough cathode with cupric sludge |
| CN104233370A (en) * | 2014-09-02 | 2014-12-24 | 肇庆市飞南金属有限公司 | Method for producing electrolytic copper by utilizing copper-containing sludge |
| CN104829058A (en) * | 2015-05-08 | 2015-08-12 | 杭州师范大学 | Simultaneous nitrogen removal and heavy metal recovering process method for waste water and special system for process method |
| CN105018732A (en) * | 2015-07-01 | 2015-11-04 | 夏栋 | Novel method for comprehensive recovery of etching waste liquid and waste residues |
| CN106399699A (en) * | 2016-12-19 | 2017-02-15 | 浙江富冶集团有限公司 | Process for treating sludge with copper import |
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| CN101624235A (en) * | 2009-08-11 | 2010-01-13 | 广州科城环保科技有限公司 | Application of acetobacter aceti for processing copper-containing etching waste solution |
| CN101658941A (en) * | 2009-09-24 | 2010-03-03 | 无锡市霄鹰环境科技有限公司 | Technology for extracting copper powder from waste materials generated in circuit board manufacturing plants by compound extraction method |
| CN102433437A (en) * | 2011-10-26 | 2012-05-02 | 惠州Tcl环境科技有限公司 | Heavy metal sludge recycling and innocent treatment method |
| CN102758090A (en) * | 2012-06-29 | 2012-10-31 | 中国瑞林工程技术有限公司 | Treatment method for electroplating sludge |
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| CN104829058A (en) * | 2015-05-08 | 2015-08-12 | 杭州师范大学 | Simultaneous nitrogen removal and heavy metal recovering process method for waste water and special system for process method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107828974A (en) * | 2017-10-23 | 2018-03-23 | 广东绿晟环保股份有限公司 | A kind of waste printed circuit board combined treatment process |
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