CN101116909A - Method for preparing copper cladded iron composite powder - Google Patents
Method for preparing copper cladded iron composite powder Download PDFInfo
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- CN101116909A CN101116909A CNA2007100766487A CN200710076648A CN101116909A CN 101116909 A CN101116909 A CN 101116909A CN A2007100766487 A CNA2007100766487 A CN A2007100766487A CN 200710076648 A CN200710076648 A CN 200710076648A CN 101116909 A CN101116909 A CN 101116909A
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Abstract
A preparation method of copper-clad iron composite powder which includes procedures as follow: the alcaline etching waste liquor containing copper is added into the acid etching waste liquor, thus feed solution with pH between 2 and 4.5 is obtained and the concentration of copper between 50 and 100g/L. The reduced iron powder is washed by acid, delivered to a reaction kettle with turbine type stirring, added with water with stirring, added orderly with dispersant agent and inhibitor and evenly with feed solution containing copper with continuous stirring, making the copper completely cladding the surface of the iron powder grain, thus copper-clad iron composite powder is obtained. Then the copper-clad iron composite powder is subject to pumping filtration, washing, centrifugal dehydration, antioxidation treatment, vacuum drying and screen separation, thus termination production is obtained. The method of the invention can make the copper evenly, tightly, firmly and completely cladding the iron powder grain, and not be oxidized for six months of storage, thus increasing the oxidation resistance. The prepared copper-clad iron powder by the invention has bright surface colour and lustre, high cladding rate, even and compact surface cladding, futhermore, the cost is lower compared with prior preparation methods because of avoiding using copper sulfate.
Description
[technical field]
The present invention relates to produce the preparation method of the required metal dust of oiliness bearing, particularly relate to a kind of method of directly utilizing printed circuit board industry etching waste liquor to prepare copper-clad iron-based composite metal powder.
[background technology]
Oiliness bearing is compared with traditional ball bearing, has advantages such as with low cost, designs simplification.Along with the progressively expansion of powder metallurgy range of application, the use of the oiliness bearing of one of mainly using as powder metallurgy also more and more widely, by 1999, the total output of China's oiliness bearing just reached 2,500,000,000.Therefore, produce the required raw material-metal dust of oiliness bearing and also increase sharply, and the kind of metal dust develops into composite powder gradually from mixed powder, alloyed powder.The oiliness bearing of China's metal dust all adopts bronze powder manufacturing at present, and the copper based articles of bronze powder production causes product price higher owing to the prices of raw and semifnished materials are high on the one hand, on the other hand because bronze powder is leaded, according to present environmental requirement, the copper based articles should be no leadwork as far as possible, therefore, be subjected to more serious restriction with bronze powder manufactured copper based articles.Copper-coated iron composite powder is the ideal material of the production oiliness bearing developed in recent years, and it is based on iron powder, coats one deck copper film at its particle surface, forms a kind of appearance color iron-based composite powder the same with copper powder.Compare with the oiliness bearing of making of bronze powder with the oiliness bearing of copper-coated iron composite powder production, not only compliance with environmental protection requirements, and price is much lower, thereby is used widely and promotes.
What the production method of existing copper-coated iron composite powder adopted is diffusion method, it is that copper powder and reduced iron powder are mixed according to a certain percentage, be heated to certain temperature then, make the copper powder fusing and be coated on the ferrous powder granules surface, because this method is that a kind of mode with physics is the surface of copper clad at ferrous powder granules, therefore exist following deficiency: 1, because the density of copper powder and iron powder is different, be prone to segregation during mixing, cause the copper skewness, therefore, during the copper clad ferrous powder granules, it is inhomogeneous easily to produce the copper clad iron powder, coats not exclusively even does not coat fully, causes the product appearance color inhomogeneous, easily oxidation, the oiliness bearing of production causes noise excessive because of starting current is excessive.2, owing to contact not closely between copper and the iron, easily wherein, cause the copper film bubbling and come off the gas parcel.
Chinese patent CN1209216C discloses a kind of manufacture method of copper-coated iron composite powder, similarly, the CN200510057231.7 application for a patent for invention discloses a kind of manufacture method of copper-coated iron composite powder, two kinds of methods all are under the state that stirs, reduced iron powder is added reaction formation copper-coated iron composite powder in the copper-bath that is mixed with stabilizing agent rapidly, after sedimentation, washing, dehydration, drying, screening, carry out anti-oxidation processing and obtain product again.The method of its anti-oxidation processing is to add stearate or benzotriazole in composite powder.Though said method has solved diffusion method production of copper cladding iron powder shortcoming inhomogeneous, that not exclusively even not do not coat, can make copper evenly, closely, be coated on the ferrous powder granules fully securely, but in process of production, because the reaction speed of iron replacement copper ion is very fast, whole coating reaction process only needs 2～10 minutes, and because of the addition sequence life period of iron powder poor, the copper of the iron powder coating that adds earlier is more, the copper of the iron powder coating that adds at last is more, therefore still has the uneven problem of copper clad iron powder.Said method directly adds zinc stearate or benzotriazole and carries out anti-oxidation processing in composite powder, because the antioxidant addition is few, specific gravity difference is big, therefore zinc stearate or benzotriazole can not be dispersed in the composite powder, more impossiblely evenly be wrapped in the composite powder surface, thereby directly influence the anti-oxidation performance of composite powder.
On the other hand, the printed circuit board industry can produce a large amount of copper-containing etching waste solutions in etching and processing printed circuit board process at present, and only annual just generation the in area, Pearl River Delta surpasses 200,000 tons of etching waste liquors.Because etching waste liquor contains the copper ion and the ammonium chloride of high concentration (being about 5%-15%), do not handle and to form serious water environment pollution hidden danger, belong to national hazardous waste, and etching waste liquor ammonium chloride is very strong to the corrosive power of metallic copper and iron, can not be directly used in the manufacturing copper-coated iron composite powder.
The CN200610038080.5 application for a patent for invention discloses a kind of method that reclaims hydrochloric acid and copper sulphate from acidic etching liquid, this method is to add the concentrated sulfuric acid at acidic etching waste liquid, reclaim hydrochloric acid by adding thermal distillation, distillation test residue adds water cooling and separates out cupric sulphate crystal, obtains product copper sulphate.Utilize etching waste liquor production copper sulphate, copper sulphate to be used further to make copper-coated iron composite powder, though technology is possible, have whole long flow path, complex process, the defective that manufacturing cost is high.
[summary of the invention]
The present invention is intended to address the above problem, and provides a kind of etching waste liquor that directly utilizes to be raw material, and technology is simple, and cost is lower, and copper can be coated on the ferrous powder granules evenly, closely, securely fully, the preparation method of the copper-coated iron composite powder that antioxygenic property is good.
For achieving the above object, the invention provides a kind of preparation method of copper-coated iron composite powder, this method comprises the steps:
A, under stirring condition, the cupric alkaline etching waste liquid for producing is mixed with acidic etching waste liquid, regulator solution PH is 2～4.5, is mixed with the material liquid that copper concentration is 50～100g/L;
B, with reduced iron powder wash successively, pickling, be placed on after the washing again in the reactor that the band turbine type stirs, add entry and dispersant, stirred 2～10 minutes, add corrosion inhibiter then, continue stirring 2～10 minutes;
C, under stirring condition, be that 1～5 times copper raw material liquid of iron powder quality evenly adds in the suspension of iron powder with parts by weight, continue to stir 10～15 minutes, make copper be coated on the surface of ferrous powder granules fully;
D, the composite powder of copper-clad iron is carried out suction filtration, remove solution, and add the clear water washing, until it till the no acidic and ammonium chloride;
E, through the copper-coated iron composite powder of washes clean through centrifugal dehydration, anti-oxidation processing, drying obtains product after the screening.
Among the step a, described copper-containing etching waste solution is printed circuit board industry etching waste liquor or the mantoquita that contains metal copper ion.
The preparation process of step b, c, d is to carry out under the turbine type stirring arm stirs.
What must illustrate is that among the step b, the addition of reduced iron powder determines that according to output the content of other material or component then is to determine according to the quality of reduced iron powder.
Among the step b, described dispersant is one or more a mixture of polyethylene glycol, PVP, polyvinyl alcohol, polyacrylate, and the percentage by weight of dispersant is 0.5～5% of an iron powder quality.
Among the step b, described corrosion inhibiter is one or more the mixture that is selected from thiocarbamide and the thiourea derivative, and the percetage by weight of corrosion inhibiter is the 0.1-1% of iron powder quality.Described thiocarbamide and thiourea derivative are methylthiourea, dimethyl sulfourea, tetramethyl thiourea, ethyl thiourea, diethyl thiourea, n-pro-pyl thiocarbamide, di-isopropyl thiourea, allylthiourea, phenylthiourea, tolylthiourea, chlorphenyl thiocarbamide or thioacetamide.
Among the step e, be that antioxidant is dissolved in the organic solvent in advance, then the organic solvent of Containing antioxidants added in the composite powder of copper-clad iron the anti-oxidation processing of composite powder.
Described antioxidant is paraffin, stearate or benzotriazole, and organic solvent is for dissolving the low boiling point solvent ethanol or the acetone of above-mentioned substance, and the percentage by weight of antioxidant is the 0.1-1% of composite powder quality.
Contribution of the present invention is that it efficiently solves the problems that exist in the prior art, and for effectively utilizing printed circuit board industry etching waste liquor, for producing low cost, high-quality copper-coated iron composite powder has been opened up a new way.
In the method for the present invention, requirement is in displacement reaction, whole reaction system is a homogeneous, be that each local iron powder concentration of synchronization all is the same with copper ion concentration in the reactor, can guarantee that just copper is coated on the ferrous powder granules equably, the present invention has avoided bringing the inhomogeneous of copper clad because of the time difference that iron powder adds by adding in advance in the reactor as the iron powder of matrix for this reason; By in preparation process, adopting turbine type to stir, overcome because of iron powder density big, particle is little, precipitate easily, adopt defectives such as the stirring of general slurry formula or anchor formula is not easy to stir, and make turbine type stir produce the strong eddy current of similar tornado, iron powder is drawn up from the centre and, therefore produced dispersion effect preferably to radially diffusion.By adding a kind of macromolecular compound dispersant that has colloid property, can be dissolved in the water, make reaction system form colloid, help the dispersion of iron powder and hinder the iron powder reunion.Also because acidic etching liquid is a hydrochloric acid system, PH is copper chloride and the ammonium chloride that 2～4.5 soda acid mixing etching waste liquor contains high concentration, corrosive power to metallic iron and copper is very strong, adding thiocarbamide and thiourea derivative is the corrosion that corrosion inhibiter can stop chlorion, especially add under the situation of macromolecular compound dispersant, both have the corrosion that synergy stops chlorion, thereby realize directly utilizing etching waste liquor to make copper-coated iron composite powder for raw material.
The present invention has also solved the anti-oxidation problem of copper-coated iron composite powder well.By antioxidant being dissolved in lower boiling organic solvent, mix with composite powder, after solvent evaporates, antioxidant promptly evenly is wrapped in the composite powder surface again, thereby, make composite powder and oxygen isolated at the very thin antioxidant unimolecular layer membrane of composite powder surface parcel one deck.
The copper-clad iron powder of the present invention's preparation, surface color is bright, the clad ratio height, the surface coats even, fine and close.Because it is avoided use copper sulphate, so cheaper than manufacture method cost in the past.
[specific embodiment]
The following example is to further explanation of the present invention and explanation, and the present invention is not constituted any limitation.
Get 40 liters of the alkaline etching waste liquid for producing of certain circuit board plant, 60 liters of acidic etching waste liquids after two kinds of waste liquids are mixed, add 100 premium on currency, stir, and its PH is 3.0 after testing, copper concentration C u
2+50g/L; Get 50 kilograms of reduced iron powders, the sulfuric acid solution with 1% was washed 1 minute for 100 liters, washed with water afterwards 3 times; Iron powder after the washing is placed 1 cube reactor of band turbine type stirring arm, add 500 premium on currency, the unlatching turbine type stirs, add 0.3 kilogram of polyethylene glycol, stirred 5 minutes, add 0.06 kilogram of thiocarbamide, stirred 5 minutes, the speed of copper-containing solution with 0.5 liter/second is added in the reactor, add and continue to stir 10 minutes, feed liquid is put to the suction filtration groove, suction filtration after composite powder washing, centrifugal, vacuum drying, is evenly sneaked into 1 liter of acetone solvent that contains 0.1 kilogram of paraffin, vacuum drying is once more crossed 80 mesh sieves and is obtained the copper-coated iron composite powder product.
The copper-clad iron powder copper content 19% of preparation, surface coating rate surpasses 99%, the outward appearance brass, not oxidation stain half a year is placed in sealing.
Claims (8)
1. the preparation method of a copper-coated iron composite powder is characterized in that, it comprises the steps:
A, under stirring condition, the cupric alkaline etching waste liquid for producing is mixed with acidic etching waste liquid, regulator solution PH is 2～4.5, is mixed with the material liquid that copper concentration is 50～100g/L;
B, with reduced iron powder wash successively, pickling, be placed on after the washing again in the reactor that the band turbine type stirs, add entry and dispersant, stirred 2～10 minutes, add corrosion inhibiter then, continue stirring 2～10 minutes;
C, under stirring condition, be that 1～5 times copper raw material liquid of iron powder quality evenly adds in the suspension of iron powder with parts by weight, continue to stir 10～15 minutes, make copper be coated on the surface of ferrous powder granules fully;
D, the composite powder of copper-clad iron is carried out suction filtration, remove solution, and add the clear water washing, until it till the no acidic and ammonium chloride;
E, through the copper-coated iron composite powder of washes clean through centrifugal dehydration, anti-oxidation processing, drying obtains product after the screening.
2. the method for claim 1 is characterized in that, in the step (a), described copper-containing etching waste solution is printed circuit board industry etching waste liquor or the mantoquita that contains metal copper ion.
3. method as claimed in claim 2 is characterized in that, the preparation process of step (b), (c), (d) is to carry out under the turbine type stirring arm stirs.
4. method as claimed in claim 3 is characterized in that, in the step (b), described dispersant is one or more a mixture of polyethylene glycol, PVP, polyvinyl alcohol, polyacrylate, and the percentage by weight of dispersant is 0.5～5% of an iron powder quality.
5. method as claimed in claim 4 is characterized in that, in the step (b), described corrosion inhibiter is one or more the mixture that is selected from thiocarbamide and the thiourea derivative, and the percetage by weight of corrosion inhibiter is the 0.1-1% of iron powder quality.
6. method as claimed in claim 5, it is characterized in that described thiocarbamide and thiourea derivative are methylthiourea, dimethyl sulfourea, tetramethyl thiourea, ethyl thiourea, diethyl thiourea, n-pro-pyl thiocarbamide, di-isopropyl thiourea, allylthiourea, phenylthiourea, tolylthiourea, chlorphenyl thiocarbamide or thioacetamide.
7. method as claimed in claim 6 is characterized in that, in the step (e), is that antioxidant is dissolved in the organic solvent in advance to the anti-oxidation processing of composite powder, then the organic solvent of Containing antioxidants is added in the composite powder of copper-clad iron.
8. method as claimed in claim 7, it is characterized in that, described antioxidant is paraffin, stearate or benzotriazole, and organic solvent is for dissolving the low boiling point solvent ethanol or the acetone of above-mentioned substance, and the percentage by weight of antioxidant is the 0.1-1% of composite powder quality.
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| Application Number | Priority Date | Filing Date | Title |
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| CN200710076648A CN100595006C (en) | 2007-08-29 | 2007-08-29 | Method for preparing copper cladded iron composite powder |
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| CN200710076648A CN100595006C (en) | 2007-08-29 | 2007-08-29 | Method for preparing copper cladded iron composite powder |
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| CN101116909A true CN101116909A (en) | 2008-02-06 |
| CN100595006C CN100595006C (en) | 2010-03-24 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102886517A (en) * | 2012-10-30 | 2013-01-23 | 江苏雄风科技有限公司 | Method for directly producing copper and iron coated powder by using byproduct copper extract of cobalt copper ore production |
| CN105251996A (en) * | 2015-11-20 | 2016-01-20 | 中南大学 | Core-shell structure copper-coated iron nanometer composite powder and preparation method and application thereof |
| 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 |
| CN111036934A (en) * | 2019-12-03 | 2020-04-21 | 昆明理工大学 | Method and device for circularly and hermetically preparing copper-clad iron |
-
2007
- 2007-08-29 CN CN200710076648A patent/CN100595006C/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102886517A (en) * | 2012-10-30 | 2013-01-23 | 江苏雄风科技有限公司 | Method for directly producing copper and iron coated powder by using byproduct copper extract of cobalt copper ore production |
| CN105251996A (en) * | 2015-11-20 | 2016-01-20 | 中南大学 | Core-shell structure copper-coated iron nanometer composite powder and preparation method and application thereof |
| 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 |
| CN111036934A (en) * | 2019-12-03 | 2020-04-21 | 昆明理工大学 | Method and device for circularly and hermetically preparing copper-clad iron |
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| CN100595006C (en) | 2010-03-24 |
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Address after: 518105 Building A, No. 18 Industrial Avenue, Third Industrial Zone, Bitou Community, Songgang Street, Baoan District, Shenzhen City, Guangdong Province Patentee after: SHENZHEN SHENTOU ENVIRONMENT TECHNOLOGY Co.,Ltd. Address before: 518105 181 Longwei Road, xiameilin, Futian District, Shenzhen, Guangdong Province Patentee before: Shenzhen Hazardous Waste Treatment Station Co.,Ltd. Address after: 518105 181 Longwei Road, xiameilin, Futian District, Shenzhen, Guangdong Province Patentee after: Shenzhen Hazardous Waste Treatment Station Co.,Ltd. Address before: The tail Meilin road 518049 Guangdong province Shenzhen city Futian District No. 181 Patentee before: Shenzhen Hazardous Waste Treatment Station |
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Address after: 518105 building a, No.18, Industrial Avenue, third industrial zone, Bitou community, Songgang street, Bao'an District, Shenzhen City, Guangdong Province Patentee after: Shenzhen Environmental Protection Technology Group Co.,Ltd. Address before: 518105 building a, No.18, Industrial Avenue, third industrial zone, Bitou community, Songgang street, Bao'an District, Shenzhen City, Guangdong Province Patentee before: Shenzhen Environmental Protection Technology Group Co.,Ltd. Address after: 518105 building a, No.18, Industrial Avenue, third industrial zone, Bitou community, Songgang street, Bao'an District, Shenzhen City, Guangdong Province Patentee after: Shenzhen Environmental Protection Technology Group Co.,Ltd. Address before: 518105 building a, No.18, Industrial Avenue, third industrial zone, Bitou community, Songgang street, Bao'an District, Shenzhen City, Guangdong Province Patentee before: SHENZHEN SHENTOU ENVIRONMENT TECHNOLOGY Co.,Ltd. |
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