CN108753252A - A kind of method and absorbing material preparing absorbing material using copper ashes - Google Patents
A kind of method and absorbing material preparing absorbing material using copper ashes Download PDFInfo
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- CN108753252A CN108753252A CN201810742143.8A CN201810742143A CN108753252A CN 108753252 A CN108753252 A CN 108753252A CN 201810742143 A CN201810742143 A CN 201810742143A CN 108753252 A CN108753252 A CN 108753252A
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- copper ashes
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- absorbing material
- oxidation
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- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
Abstract
The present invention provides a kind of methods preparing absorbing material using copper ashes, belong to metallurgical technology field, including following preparation process：Tabletting after copper ashes is mixed with calcium oxide obtains modification copper ashes；Obtained modification copper ashes is subjected to melt oxidation, oxidation modification copper ashes is obtained, goes out not full graininess magnetic iron ore phase；Oxidation modification copper ashes is crushed successively, magnetic separation, obtains magnetisable material；Obtained magnetisable material is ground to 70~150nm, obtains absorbing material.The present invention handles copper ashes by melt oxidation method, makes iron constituent element selective enrichment in copper ashes in magnetic iron ore phase, and Fe3O4Nanocrystal is embedded in many oxide, still with a small amount of dielectricity oxide S iO after Magneto separate2, avoid Fe3O4Particle is reunited caused by magnetism, and synthetic quantity is big, it can be achieved that large-scale production.
Description
Technical field
It is the present invention relates to metallurgical technology field, more particularly to a kind of to prepare the method for absorbing material using copper ashes and inhale wave material
Material.
Background technology
A large amount of copper ashes has been accumulated every year by metallurgy of copper enterprise of China.The copper ashes in China is mainly pyrometallurgical smelting slag, additionally
There are a considerable amount of vessel slags and wet type copper smelting leached mud.A large amount of copper ashes not only land occupation, but also pollution environment, is more caused
The huge waste of resource.The typical composition of copper ashes is FeO38%~53%, SiO227%~37%, Fe3O412%~15%,
MgO 1%~3%, CaO 4%~15%, Al2O32%~12%, S 0.46%~0.79%, Cu 0.17%~0.33%.
As can be seen that TFe contents are average up to 40% or more in copper ashes, it, will be right if energy effective exploitation utilizes the iron resource in copper ashes
The sustainable development of metallurgy of copper enterprise is promoted to have an important influence on.Theoretical research and production practices show that the iron in copper ashes is main
With magnetic iron ore phase (Fe3O4), fayalite (2FeOSiO2) form exist.Fayalite is being total to for complicated silicate composition
Melt, is the complicated network crystal that Si-O atoms are connected with each other, and the effective of Si-Fe is difficult to realize using conventional mineral processing method
Separation, thus also it is difficult to realize the recycling of Fe resources.
On the other hand, electromagnetic radiation pollution has become the 4th dirt after atmosphere pollution, water pollution and noise pollution
Dye source, and be on the rise with electronics, telecommunication technology fast development.Electromagnetic wave absorbent material is considered as that solution is serious at present
The most effective approach of electromagnetic pollution problem.Nanometer Fe3O4It is a kind of with the advantages such as at low cost, design flexibility is high, absorption is strong
Very promising absorbing material.Currently, the Fe mainly synthesized by wet chemistry method3O4The absorbing material of base, central synthetic steps
For：Coprecipitation is used to prepare Fe first3O4Secondly magnetic nanoparticle prepares EG/PANI composite materials, finally utilize machinery
Blending method prepares EG/PANI/Fe3O4Composite material.But above-mentioned preparation method absorbing material in preparation process is easily reunited, and is closed
It is few at amount, it can not industrial mass production.
Invention content
In view of this, present invention aims at a kind of method preparing absorbing material using copper ashes is provided, the present invention provides
Preparation method make the iron constituent element selective enrichment in copper ashes in magnetic iron ore, avoid Fe3O4Particle is caused by magnetism
Reunite, synthetic quantity is big, it can be achieved that large-scale production.
The present invention provides a kind of methods preparing absorbing material using copper ashes, including following preparation process：
1) tabletting after mixing copper ashes with calcium oxide obtains modification copper ashes；
2) the modification copper ashes for obtaining the step 1) carries out melt oxidation, and not full graininess magnetic iron ore phase is precipitated, obtains
Copper ashes is modified to oxidation；
3) oxidation obtained in the step 2) modification copper ashes is crushed successively, magnetic separation, obtains magnetisable material；
4) obtained magnetisable material is ground to 70~150nm, obtains absorbing material.
Preferably, told copper ashes includes the material composition of following mass percentage：
Preferably, the granularity of the copper ashes<200 mesh.
Preferably, the quality of the calcium oxide in the step 1) is the 5%~10% of copper ashes quality.
Preferably, the temperature of melt oxidation is 1350 DEG C~1500 DEG C in the step 2).
Preferably, the heating rate that the temperature of melt oxidation is warming up in the step 2) is 5~10 DEG C/min.
Preferably, the oxidant of the melt oxidation is air, and the flow velocity of the air is 200mL/min~400mL/
min。
Preferably, broken granularity in the step 3)<200 mesh.
Preferably, the magnetic field intensity of magnetic separation is 100mT~200mT in the step 3).
The present invention also provides absorbing materials made from the preparation method, including following mass percentage raw material group
At：
The granularity of the absorbing material is 70~150nm.
Advantageous effects：The present invention provides a kind of methods preparing absorbing material using copper ashes, by copper ashes and oxidation
Tabletting after calcium mixing obtains modification copper ashes；Obtained modification copper ashes is subjected to melt oxidation, not full graininess magnetic iron ore is precipitated
Phase obtains oxidation modification copper ashes；Obtained oxidation modification copper ashes is crushed successively, magnetic separation, obtains magnetisable material；It will obtain
Magnetisable material be ground to 70~150nm, obtain absorbing material.The present invention handles modification copper ashes by melt oxidation method, makes copper
Iron constituent element selective enrichment in slag is in magnetic iron ore phase, and Fe3O4Nanocrystal is embedded in many oxide such as SiO2, MgO and
In CaO, still with a small amount of dielectricity oxide S iO after Magneto separate2, avoid Fe3O4Particle is rolled into a ball caused by magnetism
Poly-, synthetic quantity is big, it can be achieved that large-scale production.
Description of the drawings
Fig. 1 is the electron-microscope scanning figure of the oxidation modification copper ashes obtained in embodiment 1；
Fig. 2 is the reflection loss curve of the absorbing material obtained in embodiment 1.
Specific implementation mode
The present invention provides a kind of methods preparing absorbing material using copper ashes, including following preparation process：
1) tabletting after mixing copper ashes with calcium oxide obtains modification copper ashes；
2) the modification copper ashes for obtaining the step 1) carries out melt oxidation, and not full graininess magnetic iron ore phase is precipitated, obtains
Copper ashes is modified to oxidation；
3) oxidation obtained in the step 2) modification copper ashes is crushed successively, magnetic separation, obtains magnetisable material；
4) obtained magnetisable material is ground to 70~150nm, obtains absorbing material.
Tabletting after the present invention mixes copper ashes with calcium oxide obtains modification copper ashes.
In the present invention, the copper ashes is preferably pyrometallurgical smelting copper ashes, wet method melting copper leaching residues or vessel slag.
In the present invention, the copper ashes preferably includes the material composition of following mass percentage：
In the present invention, the iron in the copper ashes is mainly with magnetic iron ore phase Fe3O4With fayalite 2FeOSiO2Form
In the presence of.
In the present invention, the granularity of the copper ashes is preferably<200 mesh, more preferably<400 mesh.
In the present invention, the quality of the calcium oxide is preferably the 5%~10% of copper ashes quality, more preferably 7%~
8%.
In the present invention, the calcium oxide is modification agent, can promote iron olive in copper ashes after copper ashes is mixed with calcium oxide
Stone phase decomposition and generate magnetic iron ore phase.
The method that the present invention mixes copper ashes with calcium oxide is not particularly limited, and is selected well known to those skilled in the art mixed
Conjunction method.
The present invention is not particularly limited the method for tabletting, selects tabletting method well known to those skilled in the art.
After obtaining modification copper ashes, obtained modification copper ashes is carried out melt oxidation by the present invention, and not full graininess magnetic is precipitated
Iron ore phase obtains oxidation modification copper ashes.The present invention handles modification copper ashes by melt oxidation method, and the iron constituent element in copper ashes is made to select
Property is enriched in magnetic iron ore phase.
In the present invention, the temperature of the melt oxidation is preferably 1350 DEG C~1500 DEG C, more preferably 1400 DEG C~
1450 DEG C, the time of the melt oxidation is preferably 10min~30min, more preferably 15~25min.
In the present invention, the oxidant of the melt oxidation is preferably air, and the flow velocity of the air is preferably 200mL/
Min~400mL/min, more preferably 250mL/min~350mL/min.
In the present invention, the heating rate for being warming up to the melt oxidation is preferably 5~10 DEG C/min, more preferably 8 DEG C/
min。
In the present invention, include successively further preferably heat preservation after the melt oxidation, be cooled to room temperature, obtain oxidation modification copper
Slag.
In the present invention, the temperature of the temperature preferred molten oxidation of the heat preservation；The time of the heat preservation is preferably 15~
30min, more preferably 20~25min.The present invention makes ferro element have time enough to be enriched in magnetic iron ore phase by insulating process.
In the present invention, the rate of temperature fall is preferably 5~10 DEG C/min, more preferably 8 DEG C/min.
In the present invention, magnetic iron ore phase is precipitated after the cooling.
In the present invention, the magnetic iron ore phase morphology is not full graininess, and the granularity of the magnetic iron ore phase is preferably 10
~30 μm.
In the present invention, modification copper ashes is preferably placed in corundum crucible by the melt oxidation, in microwave material work station
Middle progress.
Obtain oxidation modification copper ashes after, the present invention by obtained oxidation modification copper ashes be crushed successively, magnetic separation, obtain magnetic
Property substance；
In the present invention, the broken granularity is preferably<200 mesh, more preferably<400 mesh.
In the present invention, the magnetic field intensity of the magnetic separation is preferably 100mT~200mT, more preferably 125mT~175mT.
In the present invention, the magnetic separation is preferably carried out in magnetic separation machine.
After obtaining magnetisable material, magnetisable material is ground to 70~150nm by the present invention, obtains absorbing material.
In the present invention, it is preferred to by being ground after magnetisable material and dispersant.
In the present invention, the dispersant is preferably ethyl alcohol or water, more preferably ethyl alcohol.
In the present invention, the dosage of the dispersant is preferably 10:1.
In the present invention, the granularity after the grinding is preferably 90~130nm, more preferably 100~120nm.
In the present invention, the grinding is preferably carried out in ball milling machine.
The present invention is not particularly limited the method for magnetisable material and dispersant, selects those skilled in the art known
Mixed method.
The present invention also provides the absorbing material that above-mentioned preparation method obtains, the absorbing material includes following quality percentage
It is formed containing content of starting materials：
The granularity of the absorbing material is 70~150nm.
In the present invention, the granularity granularity of the absorbing material is preferably 90~130nm, more preferably 100~120nm.
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention
Content is not limited solely to the following examples.
Embodiment 1
Copper ashes is Flash Smelting Furnace copper ashes, is specifically comprised：
By copper ashes it is broken it is broken after using 200 mesh sieve (<74 μm) screening, the 100g copper ashes after screening is mixed with 5g CaO
Tabletting after even, the modification copper ashes after tabletting is contained in corundum crucible, is placed in microwave material work station and is heated with 5 DEG C/min
To 1450 DEG C.It is passed through the air oxidation 10min of 200mL/min, 20min is kept the temperature after to be oxidized, then with the speed of 5 DEG C/min
Rate is to room temperature.Oxidation modification copper ashes is obtained, it is graininess (shown in Fig. 1), 21 μm of average particle size that magnetic iron ore, which is precipitated, mutually.Oxidation is changed
Matter copper ashes is crushed to 200 mesh hereinafter, being placed in magnetic separator, and magnetic field intensity 100mT carries out magnetic separation.Magnetisable material is placed in ball
In grinding machine, addition ethyl alcohol is dispersant, is ground for 24 hours, until Fe3O4Nanocrystal granularity is 70nm~90nm, and absorbing material is made.
Embodiment 2
Copper ashes is silver stove copper ashes, is specifically comprised：
By copper ashes it is broken it is broken after using 200 mesh sieve (<74 μm) screening, the 100g copper ashes after screening is mixed with 7g CaO
Tabletting after even, the modification copper ashes after tabletting is contained in corundum crucible, is placed in microwave material work station and is heated with 5 DEG C/min
To 1500 DEG C.It is passed through the air oxidation 20min of 400mL/min, 20min is kept the temperature after to be oxidized, then with the speed of 5 DEG C/min
Rate is to room temperature.Oxidation modification copper ashes is obtained, it is graininess, 18 μm of average particle size that magnetic iron ore, which is precipitated, mutually.Oxidation modification copper ashes is broken
200 mesh are broken to hereinafter, being placed in magnetic separator, magnetic field intensity 100mT carries out magnetic separation.Magnetisable material is placed in ball mill, is added
It is dispersant to enter ethyl alcohol, is ground for 24 hours, until Fe3O4Nanocrystal granularity is 100nm~120nm, and absorbing material is made.
Embodiment 3
Copper ashes is Ausmelt furnace copper ashes, is specifically comprised
By copper ashes it is broken it is broken after using 200 mesh sieve (<74 μm) screening, the 100g copper ashes after screening is mixed with 9g CaO
Tabletting after even, the modification copper ashes after tabletting is contained in corundum crucible, is placed in microwave material work station and is heated with 5 DEG C/min
To 1400 DEG C.It is passed through the air oxidation 20min of 300mL/min, 20min is kept the temperature after to be oxidized, then with the speed of 5 DEG C/min
Rate is to room temperature.Oxidation modification copper ashes is obtained, it is graininess, 25 μm of average particle size that magnetic iron ore, which is precipitated, mutually.Oxidation modification copper ashes is broken
200 mesh are broken to hereinafter, being placed in magnetic separator, magnetic field intensity 200mT carries out magnetic separation.Magnetisable material is placed in ball mill, is added
It is dispersant to enter ethyl alcohol, is ground for 24 hours, until Fe3O4Nanocrystal granularity is 130nm~150nm, and absorbing material is made.
The PNA-N5244A type vector network analyzers that the absorbing material obtained in embodiment 1 agilent company is produced
Test, after material and paraffin are mixed in a certain ratio, it is 2.0mm, internal diameter 3.04mm, outer diameter that mixture, which is pressed into thickness,
For the coaxial annulus of 7.00mm, test at room temperature.Fig. 2 is the reflection loss curve of absorbing material in embodiment 1.
As shown in Figure 2, the minimum reflection loss in embodiment 1 is -21dB.
The absorbing property of the absorbing material in embodiment 2~3 is measured with same method.
The absorbing material that Examples 1 to 3 is obtained carries out absorbing property evaluation, and the results are shown in Table 1.
The absorbing property of the absorbing material obtained in 1 Examples 1 to 3 of table is evaluated
| Absorbing property is evaluated | |
| Embodiment 1 | Minimum reflection loss is about -21dB |
| Embodiment 2 | Minimum reflection loss is about -20dB |
| Embodiment 3 | Minimum reflection loss is about -22dB |
As shown in Table 1, the absorbing material absorbing property prepared by Examples 1 to 3 is good.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of method preparing absorbing material using copper ashes, includes the following steps：
1) tabletting after mixing copper ashes with calcium oxide obtains modification copper ashes；
2) the modification copper ashes for obtaining the step 1) carries out melt oxidation, and not full graininess magnetic iron ore phase is precipitated, obtains oxygen
Change modification copper ashes；
3) the oxidation modification copper ashes that the step 2) obtains is crushed successively, magnetic separation, obtains magnetisable material；
4) magnetisable material that the step 3) obtains is ground to 70~150nm, obtains absorbing material.
2. according to the method described in claim 1, it is characterized in that, the copper ashes in the step 1) includes following quality percentage contains
The component of amount：
3. method according to claim 1 or 2, which is characterized in that the granularity of the copper ashes<200 mesh.
4. according to method as claimed in claim 1 or 2, which is characterized in that the quality of calcium oxide is copper ashes quality in the step 1)
5%~10%.
5. according to the method described in claim 1, it is characterized in that, in the step 2) melt oxidation temperature be 1350 DEG C~
1500℃。
6. according to the method described in claim 5, it is characterized in that, being warming up to the heating of melt oxidation temperature in the step 2)
Rate is 5~10 DEG C/min.
7. according to the method described in claim 1,5 or 6, which is characterized in that the melt oxidation carries out in air atmosphere, institute
The flow velocity for stating air is 200mL/min~400mL/min.
8. according to the method described in claim 1, it is characterized in that, the granularity being crushed in the step 3)<200 mesh.
9. according to the method described in claim 1, it is characterized in that, in the step 3) magnetic separation magnetic field intensity be 100mT~
200mT。
10. the absorbing material that preparation method as described in any one of claim 1 to 9 obtains, which is characterized in that the suction wave material
Material includes following mass percentage raw material composition：
The granularity of the absorbing material is 70~150nm.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810742143.8A CN108753252B (en) | 2018-07-09 | 2018-07-09 | Method for preparing wave-absorbing material by using copper slag and wave-absorbing material |
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|---|---|---|---|
| CN201810742143.8A CN108753252B (en) | 2018-07-09 | 2018-07-09 | Method for preparing wave-absorbing material by using copper slag and wave-absorbing material |
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| CN108753252B CN108753252B (en) | 2021-02-19 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110204352A (en) * | 2019-07-20 | 2019-09-06 | 兰州理工大学 | A kind of method that copper ashes tailing prepares magnetic hollow ceramic microsphere |
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| JP2006222105A (en) * | 2005-02-08 | 2006-08-24 | Hoshino Sansho:Kk | Process for producing filler containing ferrite, electromagnetic wave heating material, electromagnetic wave shielding material |
| CN101029355A (en) * | 2007-04-13 | 2007-09-05 | 北京科技大学 | Method for producing nano-magnetic FeO particle by iron extracted and utilized in tin tails |
| CN101597472A (en) * | 2009-07-07 | 2009-12-09 | 武汉工程大学 | A kind of method of utilizing copper iron tailings relieving haperacidity burning slag to prepare ferriferrous oxide microwave adsorbing material |
| CN104988302A (en) * | 2015-06-19 | 2015-10-21 | 兰州理工大学 | Nickel slag processing method for efficiently recovering iron resource |
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2018
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006222105A (en) * | 2005-02-08 | 2006-08-24 | Hoshino Sansho:Kk | Process for producing filler containing ferrite, electromagnetic wave heating material, electromagnetic wave shielding material |
| CN101029355A (en) * | 2007-04-13 | 2007-09-05 | 北京科技大学 | Method for producing nano-magnetic FeO particle by iron extracted and utilized in tin tails |
| CN101597472A (en) * | 2009-07-07 | 2009-12-09 | 武汉工程大学 | A kind of method of utilizing copper iron tailings relieving haperacidity burning slag to prepare ferriferrous oxide microwave adsorbing material |
| CN104988302A (en) * | 2015-06-19 | 2015-10-21 | 兰州理工大学 | Nickel slag processing method for efficiently recovering iron resource |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110204352A (en) * | 2019-07-20 | 2019-09-06 | 兰州理工大学 | A kind of method that copper ashes tailing prepares magnetic hollow ceramic microsphere |
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