CN101200003A - Preparing process for copper iron compound powder by waste cupric liquor - Google Patents
Preparing process for copper iron compound powder by waste cupric liquor Download PDFInfo
- Publication number
- CN101200003A CN101200003A CNA2006101650549A CN200610165054A CN101200003A CN 101200003 A CN101200003 A CN 101200003A CN A2006101650549 A CNA2006101650549 A CN A2006101650549A CN 200610165054 A CN200610165054 A CN 200610165054A CN 101200003 A CN101200003 A CN 101200003A
- Authority
- CN
- China
- Prior art keywords
- waste liquid
- copper
- contained waste
- powder
- iron compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The invention relates to a method for preparing copper iron compound powder by using waste cupric liquor .The steps are as follows: 1) raw material selection: waste cupric liquor and ferrous powder; 2) pretreatment: filter the waste cupric liquor, remove solid impurities and then neutralize with ammonia; thus the waste cupric liquor with PH Value of 6-8 is obtained; 3) Chemical replacement reaction: use the aid to regulate the PH value of the waste cupric liquor obtained in step 2) to 3-4; then add the ferrous powder and stir, react for 20-30 minutes at room temperature, then the sedimentation is obtained, and the supernatant fluid is recycled for further use; 4) wash the sediment obtained in step 3) with water, and then dip the sediment in the hot soap lye for 10-20 minutes, after that clean with water; 5) through dehydration, dry and deoxidizing for 2 to 3 hours to obtain copper iron compound powder. The invention can make waste cupric liquor be changed to valuables from waste; the copper iron compound powder is produced through simple replacement deoxidizing reaction, particularly the malysite reaction product generated in technical process can be taken as the raw material of a superfine FeCu series powder which can be used to produce another diamond tool. The whole technique has the advantages of simple and rational structure, strong operability, environmental protection and low cost.
Description
Technical field
The present invention relates to a kind of method for preparing copper iron compound powder with contained waste liquid, particularly a kind ofly utilize contained waste liquid as raw material, adopt the chemical replacement legal system to be equipped with the environmental protection of copper iron compound powder, energy-conservation, production technology cheaply, be mainly used in industries such as diamond tool, powder metallurgy, friction material.
Background technology
In printed circuit board (PCB) production and the production of cathode copper enterprise, contain copper ion in the waste water of discharging, a large amount of copper-containing residues are abandoned as refuse in the production of enterprises such as copper smelting plant and powder by atomization, these discarded objects directly discharge or throw away and not only make environment suffer severe contamination, also cause significant wastage.Copper is important non-ferrous metal, it is only second to steel and iron on using, China is the still importer of copper at present, is destroyed day by day and natural resources serious deficient today at ecological environment, makes full use of and develop contained waste liquid and cupric waste resource has environmental benefit and social benefit preferably.
In the printed circuit board (PCB) technological process of production, the spent etching solution of operations such as nog plate, weak burn into electro-coppering discharging contains a large amount of copper ions.According to statistics, more than 1000 families of the existing printed circuit board (PCB) enterprise of China, produced 2500～3000 cubic metres of cupric spent etching solutions in average day, every cube of copper that contains 140～150 kilograms, can reclaim 450 tons of metallic coppers every day from waste liquid, can reclaim 13.5 ten thousand tons of copper in 1 year, is equivalent to more than 10 year output of producing ten thousand tons of copper works per year, 6,000,000,000 yuan copper production value is again arranged, for country increases taxes 1,000,000,000 yuan every year.Copper ion concentration is up to 12g/l in domestic a lot of cathode copper and the electrolytic copper powder manufacturer electrolysis waste solution, most of enterprise only adds alkaline matter (as: NaOH, lime stone etc.) waste liquid acidity is handled neutrality, just discharging causes the waste of a large amount of copper resources.How to handle these waste liquids, it is turned waste into wealth also have good economic benefit.
The domestic and international demand of copper iron compound powder is big, is widely used in the bonding phase material in make powder metallurgical oiliness bearing, friction material and the diamond tool.The copper iron compound powder that utilizes chemical method to produce, its design feature is: be core with the iron powder, the surface by the fine copper even compact coating; Its goods main feature is: weight of unleaded, erosion wear resistance, low cost, reduction powder metallurgy product etc., alternative oiliness bearing copper powder, bronze powder (as: contain Pb be 3% 663 powder), iron copper mixed powder.
Its characteristic is at the oiliness bearing manufacture view, easy segregation when having overcome other powder (as: in the mode of physical diffusion the iron copper mixed powder of copper clad) processing oiliness bearing on the surface of ferrous powder granules, mechanical property instability, the shortcoming that job efficiency is low, has the alloying of being easy to, segregation does not take place in the use, the cost performance height, advantages such as goods high comprehensive performance.
In diamond tool is made, with this composite powder with other powder, as, electrolytic copper powder, Co powder, carbonyl iron dust and diamond etc. mix mutually, make the diamond cut saw blade through hot pressed sintering.Have following characteristic:
1. behind the outer evenly coating of the iron powder copper, with regard to the composition segregation that does not exist iron powder to mix with copper powder, the Fe-Cu alloying level improves after oversintering or hot pressing, thereby increases the mechanical performance of carcass.
2. by the plating of crossing of copper layer, make the various powder in the carcass material form more tabetisols altogether, can soak into bonding with diamond better at sintering or hot pressing.
3. can avoid sintering (hot pressing) iron powder causes adamantine intensity to reduce to adamantine erosion.
4. be with copper and copper hot pressing seam between the powder particle in the carcass material, improve heat transfer path, improve the carcass material thermal conductivity.
5. in fact hot pressed sintering is finished by the outer copper of copper-clad iron powder, therefore, can reduce the sintering temperatures of tens degree, thereby cuts down the consumption of energy and effectively protect the intensity of diamond particles.
At present, the copper iron compound powder production technology mainly is to adopt copper sulphate and iron powder to make raw material, at a certain temperature, adds specific stabilizing agent, and the copper in the copper-bath is replaced on the ferrous powder granules.Its complex process, per kilogram cost are at 17～20 yuan, and the FeSO that produces
4The process for treating waste liquor complexity, the cost height.
Summary of the invention
Purpose of the present invention just provides and a kind ofly prepares the method for copper iron compound powder, particularly a kind of environmental protection, energy-conservation, low cost method that adopts the chemical replacement legal system to be equipped with copper iron compound powder with contained waste liquid.
The objective of the invention is to be achieved through the following technical solutions.
A kind ofly prepare the method for copper iron compound powder with contained waste liquid, its step is as follows:
(1) raw material is selected: contained waste liquid and iron powder;
(2) preliminary treatment: with contained waste liquid solids removed by filtration impurity, with the ammoniacal liquor neutralization, getting pH value is the contained waste liquid of 6-8 then;
(3) chemical replacement reaction: the PH with the described contained waste liquid of sour set-up procedure (2) is 3-4, adds iron powder and stirring then, and reaction is 20-30 minute under the room temperature, must precipitate, and supernatant reclaims standby;
(4) step (3) gained precipitated product is washed with water, the reusable heat soap lye soaked after 10-20 minute, washed;
(5) drying: through dehydration, dry 2～3 hours of reduction gets copper iron compound powder.
A kind of optimal technical scheme is characterized in that: used contained waste liquid is an electrolysis waste solution, or the printed circuit board etching solution, or the cupric waste is dissolved in sour gained.
Described contained waste liquid is generally CuSO
4Waste liquid or CuCl
2Waste liquid, the most frequently used CuSO
4Waste liquid.Allow the existence of metal ions such as a spot of Zn, Fe, Ni in the contained waste liquid.
A kind of optimal technical scheme is characterized in that: the copper ion concentration of the contained waste liquid after described step (2) preliminary treatment is 0.08mol/l～0.48mol/l; Calculated relationship between the weight of the iron powder that the volume of this contained waste liquid and step (3) are added is: the volume of copper ion molar concentration (mol/l) * this contained waste liquid in iron powder weight=0.312 of adding * this contained waste liquid.
A kind of optimal technical scheme, it is characterized in that: the copper ion concentration of the contained waste liquid after described step (2) is handled is preferably 0.24mol/l～0.48mol/l, and the calculated relationship between the weight of the iron powder that the volume of this contained waste liquid and step (3) are added is: the volume of copper ion molar concentration (mol/l) * this contained waste liquid in iron powder weight=0.312 of adding * this contained waste liquid.
A kind of optimal technical scheme, it is characterized in that: the used acid of described step (3) is acetic acid, its addition is: the copper ion concentration of the contained waste liquid before described step (2) is handled is between 0.08mol/l～0.2mol/l the time, and every liter of solution adds 5～6ml acetic acid; The copper ion concentration of the contained waste liquid before described step (2) is handled is between 0.24mol/l～0.28mol/l the time, and every liter of solution adds 8～10ml acetic acid; The copper ion concentration of the contained waste liquid before described step (2) is handled is between 0.32mol/l～0.48mol/l the time, and every liter of solution adds 15～20ml acetic acid.
A kind of optimal technical scheme is characterized in that: the water described in described the washing with water in the described step (4) is deionized water, washs several times, does not have SO in cleaning solution
4 2-Till the existence; The additional proportion of soap is in the described hot soap lye: add 50～150g soap in the 100kg copper iron compound powder.
A kind of optimal technical scheme is characterized in that: the temperature the when drying of the gained copper iron compound powder in the described step (4) is reduced is between 450 ℃～580 ℃.
A kind of optimal technical scheme is characterized in that: the gained copper iron compound powder in the described step (4) is-100 orders or-200 orders, and copper content is 18～22 weight %.
A kind of optimal technical scheme, it is characterized in that: with the oversize at the gained copper iron compound powder end in the described step (4), Mechanical Crushing becomes-100 orders or-200 purpose powder to join in the copper-bath that configures, and then repeats step (3)-(4) in the claim 1.
A kind of optimal technical scheme is characterized in that: in the described copper-bath 0.2～0.5 times of the powder weight of the amount of copper sulphate after for the fragmentation that adds.
A kind of optimal technical scheme is characterized in that: the gained copper iron compound powder is-100 orders or-200 orders, and copper content is 25～30 weight %.
Raw materials technology of the present invention is a contained waste liquid, by simple displacement reduction reaction production of copper iron composite powder at room temperature, not only turn waste into wealth, and production cost is low.The molysite product that particularly produces in the technological process can be used as the raw material of producing the ultra-fine FeCu series powder that another kind of diamond tool uses, and bringing metal ions such as a spot of Zn, Fe, Ni in the supernatant into by waste liquid, is beneficial element in the ultra-fine FeCu series powder.So the technology that the present invention relates to has advantages of simple, strong operability, environmental protection, energy-conservation, advantage cheaply.
The invention will be further described below in conjunction with embodiment, but and do not mean that limiting the scope of the invention.
The specific embodiment
Embodiment 1:
Filter out solid impurity in the electrolysis waste solution, 1000 liters of power taking liquid waste solutions, copper ion concentration are 0.2mol/l, use in the ammoniacal liquor and waste liquor PH value to 6.5; The acetic acid that adds 6 liters in the waste liquid after the processing stirs, and its pH value is 3.5; Add 63kg in solution, (pine is than being 2.35g/cm for-200 purpose reduced iron powders
3), stirring reaction 30 minutes, post precipitation reclaims supernatant standby, and the powder of post precipitation spends deionised water, does not have SO in cleaning solution
4 2-Exist, use hot soap lye (containing soap 100g) to soak then 20 minutes, behind the wash clean, processed, dry reduced powder, final sizing, packing, and do anti-oxidation processing.Promptly make-200 order copper iron compound powder 64.6kg, copper content is 20.5%, and pine is than being 1.90g/cm
3
Embodiment 2:
Filter out solid impurity in the etching solution such as printed circuit board (PCB), 2000 liters of power taking liquid waste solutions, copper ion concentration are 0.35mol/l, rise, with in the ammoniacal liquor and acid solution pH value to 6.0; The acetic acid that adds 35 liters in the waste liquid after the processing stirs, and its pH value is 3.0; Add 219kg in solution, (pine is than being 2.5g/cm for-200 purpose reduced iron powders
3), stirring reaction 28 minutes, post precipitation reclaims supernatant standby, and the powder of post precipitation spends deionised water, does not have SO in cleaning solution
4 2-Exist Deng impurity, use hot soap lye (containing soap 250g) to soak then 20 minutes, behind the wash clean, processed, dry reduced powder, final sizing, packing, and do anti-oxidation processing.Promptly make-200 order copper iron compound powder 224kg, copper content is 19.8%, and pine is than being 2.05g/cm
3
Embodiment 3:
The copper-containing residue that the powder by atomization intermediate frequency furnace produces, the contained waste liquid that obtains after sulfuric acid treatment filters out solid impurity in the waste liquid, gets 2000 liters, and copper ion concentration is 0.45mol/l, uses in the ammoniacal liquor and acid solution pH value to 8; The acetic acid that adds 40 liters in the waste liquid after the processing stirs, and its pH value is 4.0; Add 281kg in solution, (pine is than being 2.7g/cm for-100 purpose reduced iron powders
3), stirring reaction 25 minutes, post precipitation reclaims supernatant standby, and the powder of post precipitation spends deionised water, does not have SO in cleaning solution
4 2-Exist Deng impurity, use hot soap lye (containing soap 250g) to soak then 20 minutes, behind the wash clean, processed, dry reduced powder, final sizing, packing, and do anti-oxidation processing.Promptly make-100 order copper iron compound powder 287kg, copper content is 21.5%, and pine is than being 2.3g/cm
3
Embodiment 4:
After the copper iron compound powder fragmentation of the cupric 19.5% that embodiment 3 is prepared, sieve-100 purpose powder, get 100kg.Preparation CuSO
4500 liters of solution, sulfur acid copper 30kg is at CuSO
4Solution adds 7.5 liters of acetic acid, stirs; With 100kg, the broken powder of-100 purposes joins in the solution, stirring reaction 20 minutes, and post precipitation reclaims supernatant standby, and the powder of post precipitation spends deionised water, does not have SO in cleaning solution
4 2-Exist, use hot soap water (containing soap 150g) to soak then 20 minutes, behind the wash clean, processed, dry reduced powder, final sizing, packing, and do anti-oxidation processing.Promptly make-100 order copper iron compound powder 105.5kg, copper content is 27.6%.
Claims (11)
1. one kind prepares the method for copper iron compound powder with contained waste liquid, and its step is as follows:
(1) raw material is selected: contained waste liquid and iron powder;
(2) preliminary treatment: with contained waste liquid solids removed by filtration impurity, with the ammoniacal liquor neutralization, getting pH value is the contained waste liquid of 6-8 then;
(3) chemical replacement reaction: the PH with sour set-up procedure (2) gained contained waste liquid is 3-4, adds iron powder and stirring then, and reaction is 20-30 minute under the room temperature, must precipitate, and supernatant reclaims standby;
(4) step (3) gained precipitated product is washed with water, the reusable heat soap lye soaked 10-20 minute, washed; Through dehydration, dry 2～3 hours of reduction gets copper iron compound powder.
2. as claimed in claim 1ly prepare the method for copper iron compound powder with contained waste liquid, it is characterized in that: the described contained waste liquid of described step (1) is an electrolysis waste solution, or the printed circuit board etching solution, or the cupric waste is dissolved in sour gained.
3. the method for preparing copper iron compound powder with contained waste liquid as claimed in claim 2, it is characterized in that: the copper ion concentration of the contained waste liquid after described step (2) preliminary treatment is 0.08mol/l～0.48mol/l, and the calculated relationship between the weight of the iron powder that the volume of this contained waste liquid and step (3) are added is: the volume of copper ion molar concentration (mol/l) * this contained waste liquid in iron powder weight=0.312 of adding * this contained waste liquid.
4. the method for preparing copper iron compound powder with contained waste liquid as claimed in claim 1, it is characterized in that: the copper ion concentration of the contained waste liquid after described step (2) is handled is 0.24mol/l～0.48mol/l, and the calculated relationship between the weight of the iron powder that the volume of this contained waste liquid and step (3) are added is: the volume of copper ion molar concentration (mol/l) * this contained waste liquid in iron powder weight=0.312 of adding * this contained waste liquid.
5. the method for preparing copper iron compound powder with contained waste liquid as claimed in claim 1, it is characterized in that: the used acid of described step (3) is acetic acid, its addition is: the copper ion concentration of the contained waste liquid before described step (2) is handled is between 0.08mol/l～0.2mol/l the time, and every liter of solution adds 5～6ml acetic acid; The copper ion concentration of the contained waste liquid before described step (2) is handled is between 0.24mol/l～0.28mol/l the time, and every liter of solution adds 8～10ml acetic acid; The copper ion concentration of the contained waste liquid before described step (2) is handled is between 0.32mol/l～0.48mol/l the time, and every liter of solution adds 15～20ml acetic acid.
6. as claimed in claim 1ly prepare the method for copper iron compound powder with contained waste liquid, it is characterized in that: the water described in described the washing with water in the described step (4) is deionized water, washs several times, does not have SO in cleaning solution
4 2-Till the existence; The additional proportion of soap is in the described hot soap lye: add 50～150g soap in the 100kg copper iron compound powder.
7. as claimed in claim 1ly prepare the method for copper iron compound powder with contained waste liquid, it is characterized in that: the temperature during the drying reduction of the gained copper iron compound powder in the described step (4) is between 450 ℃～580 ℃.
8. as claimed in claim 1ly prepare the method for copper iron compound powder with contained waste liquid, it is characterized in that: the gained copper iron compound powder in the described step (4) is-100 orders or-200 orders, and copper content is 18～22 weight %.
9. the method for preparing copper iron compound powder with contained waste liquid as claimed in claim 8, it is characterized in that: with the oversize at the gained copper iron compound powder end in the described step (4), Mechanical Crushing becomes-100 orders or-200 purpose powder to join in the copper-bath that configures, and then repeats step (3)-(4) in the claim 1.
10. as claimed in claim 9ly prepare the method for copper iron compound powder, it is characterized in that: in the described copper-bath 0.2～0.5 times of the powder weight of the amount of copper sulphate after for the fragmentation that adds with contained waste liquid.
11. as claimed in claim 9ly prepare the method for copper iron compound powder with contained waste liquid, it is characterized in that: the gained copper iron compound powder is-100 orders or-200 orders, copper content is 25～30 weight %.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006101650549A CN101200003A (en) | 2006-12-12 | 2006-12-12 | Preparing process for copper iron compound powder by waste cupric liquor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006101650549A CN101200003A (en) | 2006-12-12 | 2006-12-12 | Preparing process for copper iron compound powder by waste cupric liquor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101200003A true CN101200003A (en) | 2008-06-18 |
Family
ID=39515466
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006101650549A Pending CN101200003A (en) | 2006-12-12 | 2006-12-12 | Preparing process for copper iron compound powder by waste cupric liquor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101200003A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103128273A (en) * | 2011-11-28 | 2013-06-05 | 重庆华浩冶炼有限公司 | Saponification method of copper powder production |
| CN105562713A (en) * | 2016-01-30 | 2016-05-11 | 常州市君成机械有限公司 | Preparing method for copper coated iron composite powder |
| CN106077623A (en) * | 2016-07-19 | 2016-11-09 | 仇颖莹 | A kind of preparation method being evenly coated copper-coated iron composite powder |
| CN108746602A (en) * | 2018-05-26 | 2018-11-06 | 烟台大学 | A method of preparing copper-clad iron powder using copper-containing wastewater |
-
2006
- 2006-12-12 CN CNA2006101650549A patent/CN101200003A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103128273A (en) * | 2011-11-28 | 2013-06-05 | 重庆华浩冶炼有限公司 | Saponification method of copper powder production |
| CN103128273B (en) * | 2011-11-28 | 2018-08-14 | 重庆有研重冶新材料有限公司 | A kind of method for saponification of copper powder production |
| CN105562713A (en) * | 2016-01-30 | 2016-05-11 | 常州市君成机械有限公司 | Preparing method for copper coated iron composite powder |
| CN106077623A (en) * | 2016-07-19 | 2016-11-09 | 仇颖莹 | A kind of preparation method being evenly coated copper-coated iron composite powder |
| CN108746602A (en) * | 2018-05-26 | 2018-11-06 | 烟台大学 | A method of preparing copper-clad iron powder using copper-containing wastewater |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101392325B (en) | Method for extracting gold from waste printed circuit board | |
| CN101928840B (en) | Method for recovering gold and silver from waste circuit boards | |
| CN102220493B (en) | Method and device for purifying zinc sulfate solution based on action of cavitation effect | |
| CN107630146A (en) | nickel recovery method | |
| JP2022509811A (en) | Battery recycling by injecting hydrogen gas into the leachate | |
| CN110819821B (en) | Method for intensively purifying zinc sulfate solution | |
| CN106868307A (en) | A kind of pyrite cinder arsenic removal is enriched with the comprehensive utilization process of gold and silver | |
| CN106381392B (en) | A kind of chemical mineral processing preprocess method of the more metal dusts of old circuit board | |
| CN102719675A (en) | Method for comprehensively recovering zinc, lead and silver from waste residues generated in zinc smelting | |
| CN100417475C (en) | Production of metal zinc powder from zinc dust and zinc dross | |
| CN101200003A (en) | Preparing process for copper iron compound powder by waste cupric liquor | |
| CN110550611A (en) | Method for efficiently leaching tellurium from copper separating slag of copper anode slime enhanced by external field effect | |
| CN101863516B (en) | Method for recovering ferrite containing chromium and nickel in stainless steel pickling waste water sludge | |
| CN102108447A (en) | Technology for removing iron and arsenic from leaching solution of purification slag generated in zinc hydrometallurgy | |
| CN108034823A (en) | A kind of method that molybdenum and copper are recycled in the molybdenum removal slag from Tungsten smelting | |
| JP4147246B2 (en) | Method for recovering metallic copper from waste liquid containing copper chloride | |
| CN109750163A (en) | A kind of method of tertiary cathode material and iron lithium anode material synthetical recovery | |
| CN102070436A (en) | Method for recovering oxalate and acid liquor from acidic etching waste liquor | |
| CN108160683A (en) | A kind of method that waste and old tin plating copper-clad plate resource utilization utilizes | |
| CN105385853B (en) | A kind of cupric gives up the processing method of magnesia brick | |
| CN111057853A (en) | Method for efficiently recovering multiple valuable substances from waste diamond tool bit raw materials | |
| CN109207735A (en) | A method of recycling zinc from discarded galvanized sheet | |
| CN204639140U (en) | A kind of equipment preparing PCB high connductivity Nano Silver | |
| CN102864304B (en) | Ultrasonic dechlorination method by supplying copper ions with copper oxide ore | |
| Ryder et al. | Environmentally Sustainable Solvent-based Process Chemistry for Metals in Printed Circuit Boards |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Open date: 20080618 |