CN106191503B - A kind of method of bi content in reduction brass - Google Patents
A kind of method of bi content in reduction brass Download PDFInfo
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- CN106191503B CN106191503B CN201610752991.8A CN201610752991A CN106191503B CN 106191503 B CN106191503 B CN 106191503B CN 201610752991 A CN201610752991 A CN 201610752991A CN 106191503 B CN106191503 B CN 106191503B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/06—Making non-ferrous alloys with the use of special agents for refining or deoxidising
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
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- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
It is a kind of to reduce bi content in brass, and then reach the method for the illeffects and regeneration that eliminate bismuth the invention discloses a kind of method for reducing bi content in brass.The characteristics of this method is that addition can form compound with bismuth in brass alloys（Such as：BixMey）Drop bismuth additive, the compound of formation is removed from melt as impurity by high-temperature physics metallurgical method, the bi content in reduction brass alloys matrix and the purpose of improvement alloy structure and processing characteristics is reached.
Description
Technical field
It is specially bismuth in a kind of reduction brass reclaimed materials the present invention relates to a kind of regeneration processing method of bismuth yellow brass
The method of content, is related to nonferrous materials processing and manufacturing field.
Background technology
Ledrite has good cutting ability and cheap price advantage, has at home and abroad obtained boundless answer
With, but there is great threat to environment for human survival containing 1~3% heavy metal lead in ledrite.In recent years, with people
Continuous enhancing to environmental protection consciousness, the application of ledrite is limited by domestic and international majority state, especially in flourishing state
Family is restricted more strict.Lead is replaced with nontoxic or low harmful toxic matter, is the main path for reducing lead contamination, at present country's external-open
The lead-free reflow of hair is mostly using bismuth as main alloying element, such as patent： 200710098481.4（Bi0.1~1.0%）；
200510050425.4（Bi0.3~1.5%）；200710035912.2（Bi0.2~1.5%）； 200810181180.2（Bi0.1
~2.5%）；200810090868.x（Bi0.3~4.0%）；200310109162.0（Bi0.1~3.5%）；
200710067480.3（Bi0.6~2.5%）Deng the main brass that Bi brass has been researched and developed and applied as replacement ledrite
Alloy.
But, during the recycling of waste and old brass, Bi brass is easily difficult to differentiate between with basis brass batch mixing, and is made
Processing factory's melting and casting is sent to for basis brass waste material, due to bismuth fusing point（271℃）Copper, zinc are significantly less than, in process of setting
On the crystal boundary for being distributed in brass ingot casting, and the cracking generation waste product of ingot casting in process, this is reclaimed again to bismuth yellow brass
Make profits with bringing extreme difficulties.Therefore, bi content is with recycling treatment technology in research and development reduction brass, to brass resource
Recovery and reusing and recycling have important practical significance.
The content of the invention
It is an object of the invention to provide a kind of method that can effectively reduce bi content in brass；Concrete technical scheme is：
The invention provides a kind of method that can effectively reduce bi content in bismuth yellow brass, comprise the following steps that：
1）Bismuth yellow brass, heating fusing are added in smelting furnace；
2）And covered with coverture；
3）Add reduction bismuth yellow brass in bi content additive, addition for the bismuth yellow brass weight 1.0~
3.5%, melting, alloying；
4）Cleaner is added, is incubated, stands, taking off miscellaneous；
5）Carry out alloy casting.
Further, step 2) described in coverture be any of graphite, charcoal, borax, ice crystal or appoint several
Combination, the thickness of coverture is 30~50 millimeters.
Further, step 4）Described in cleaner be sodium fluoride or calcirm-fluoride, or sodium fluoride and calcirm-fluoride mixture.
Further, step 3）Middle smelting temperature is 1000~1150 DEG C, and smelting time is 30~40 minutes.
Further, step 5）Middle cast temperature is not less than 950 DEG C.
Further, step 5）Middle cast temperature is between 950~1050 DEG C.
Further, step 4）Middle time of repose is 10~20 minutes.
Further, step 4）The addition of middle cleaner is the 0.1~0.5% of the bismuth yellow brass weight.
Additive is made up of major ingredient, auxiliary material and the second auxiliary material；The major ingredient is by a kind of middle chemical combination in lithium, calcium, strontium, barium
The composition of thing or a variety of intermediate compounds, it is 60~70% that major ingredient, which accounts for weight of additive percentage,；The auxiliary material by cerium, yttrium,
One or more of mixing compositions in the oxide of lanthanum, the percentage by weight that auxiliary material accounts for additive is 10~30%；Described second is auxiliary
Material is made up of the one or more in Boratex, sodium chloride, sodium carbonate, the second auxiliary material account for the percentage by weight of additive for 10~
20%。
Physical Metallurgy is combined by the present invention with Alloying Treatment brass alloys technology, is reclaimed for Bi brass with making profits again
With this method has except the characteristics of bismuth effect is good, technique is simple, processing cost is low, through the bismuth-brass alloy after the technical finesse
Material is used available for reproduction.The present invention can be used for the recycling and regeneration of bismuth yellow brass waste material, be a kind of ring
The friendly recycling economy processing method in border, it is possible to resolve existing Bi brass material processes problem, while the Bi brass after processing
It can reapply in mechanical manufacturing field, with significant economic benefit and social benefit.
Embodiment
Further to illustrate the present invention to reach technological means and effect that predetermined goal of the invention is taken, below in conjunction with
Embodiment, principle, feature and effect to the present invention are described in detail as after.
The method of bi content in the reduction brass of the present invention, is that a kind of Bi brass is reclaimed and regeneration method.Its principle
It is to add the additive for dropping bismuth in the brass of high temperature melting, additive can form the less immobilization of proportion in the liquid phase with bismuth
Compound.With the reduction of melt temperature, then the solid-phase compound added in the cleaner with cohesion, brass melt is continuous
Increase, float up to brass alloys liquid level, be gathered into the larger solid compounds of particle, compound is removed using miscellaneous method is taken off.
Therefore, the brass old material of recovery and the drop bismuth additive developed are heated to 1000~1150 DEG C, in high-temperature physics metallurgical process
Middle progress melting, alloying process processing, can reach the content and Bi brass recycling purpose of reduction bismuth.
Wherein additive is made up of major ingredient, auxiliary material and the second auxiliary material；The major ingredient is in the middle of one kind in lithium, calcium, strontium, barium
The composition of compound or a variety of intermediate compounds, it is 60~70% that major ingredient, which accounts for weight of additive percentage,；The auxiliary material is by rare earth
One or more of mixing compositions in cerium, yttrium, the oxide of lanthanum, the percentage by weight that auxiliary material accounts for additive is 10~30%；It is described
Second auxiliary material is made up of the one or more in Boratex, sodium chloride, sodium carbonate, and the second auxiliary material accounts for the percentage by weight of additive
For 10~20%.Mutual replacement in major ingredient, auxiliary material and the second auxiliary material inside composition, which can be played, preferably removes bismuth effect.
Embodiment 1
In order to investigate effect, the bi content of brass old material is detected first, through surveying this batch of brass old material bi content
0.84%.Additive is 70% major ingredient by percentage by weight, and the auxiliary material and percentage by weight that percentage by weight is 20% are the of 10%
Two auxiliary materials are constituted.Cleaner selects sodium fluoride, can also select calcirm-fluoride, or sodium fluoride is mixed with calcirm-fluoride with arbitrary proportion
Close.Coverture can use one of which from graphite flake or the graphite of powdery, or charcoal, borax, ice crystal,
Can also by it is several mixed with arbitrary proportion after use.
Operated as follows：
1）Bi brass old material, heating fusing are added in smelting furnace；
2）Brass old material liquation is covered as coverture with graphite flake, the thickness of coverture is 30 millimeters；
3）Ready additive is added, addition is the 1.0% of brass old material weight, together melting, alloying, control
Smelting temperature is 1050 DEG C, melting 30 minutes；Uniform stirring promotes alloying process uniform in fusion process；
4）Sodium fluoride is added as cleaner, weight for brass old material weight 0.2%, insulation stand 15 minutes, through except
Gas, take off miscellaneous；
5）950 DEG C are cooled to, 1000 DEG C can also be cooled to, ingot casting is cast into.
It is 0.0417% that sampling analysis, which obtains bi content in sample, and it is 95% to be computed drop bismuth rate.Table 1 is the work in embodiment
Skill parameter and drop bismuth effect.
| Bismuth additive drops | Cleaner | Smelting temperature | Smelting time | Time of repose | Bismuth rate drops |
| 1.0% | 0.2% | 1050℃ | 30min | 15min | 95% |
Table 1
Embodiment 2
This batch of brass old material bi content 0.84%.Additive preparation, using by the major ingredient that percentage by weight is 70%, weight hundred
Divide the additive of the auxiliary material that ratio is 10% and the second auxiliary material that percentage by weight is 20% composition.Cleaner selects sodium fluoride, also may be used
To select calcirm-fluoride, or sodium fluoride mixed with calcirm-fluoride with arbitrary proportion.Coverture selects graphite flake or powdery
Graphite, or charcoal, borax, ice crystal can use one of which, can also by it is several mixed with arbitrary proportion after make
With.
Operated as follows：
1）Bi brass old material, heating fusing are added in smelting furnace；
2）Brass old material liquation is covered as coverture with graphite flake, the thickness of coverture is 50 millimeters；
3）Ready additive is added, addition is the 1.5% of brass old material weight, together melting, alloying, control
Smelting temperature is 1100 DEG C, melting 35 minutes；Uniform stirring promotes alloying process uniform in fusion process；
4）Sodium fluoride is added as cleaner, weight for brass old material weight 0.25%, insulation stand 10 minutes, through except
Gas, take off miscellaneous；
5）1000 DEG C are cooled to, 1050 DEG C can be also cooled to, be cast into ingot casting.
It is 0.0452% that sampling analysis, which obtains bi content in sample, and it is 94.6% to be computed drop bismuth rate.Table 2 is in embodiment
Technological parameter and drop bismuth effect.
| Bismuth additive drops | Cleaner | Smelting temperature | Smelting time | Time of repose | Bismuth rate drops |
| 1.5% | 0.25% | 1100℃ | 35min | 10min | 94.6% |
Table 2
Embodiment 3
This batch of brass old material bi content 0.78%.Additive preparation, using by the major ingredient that percentage by weight is 60%, weight hundred
Divide the additive of the auxiliary material that ratio is 30% and the second auxiliary material that percentage by weight is 10% composition.Cleaner selects sodium fluoride, also may be used
To select calcirm-fluoride, or sodium fluoride mixed with calcirm-fluoride with arbitrary proportion.Coverture selects graphite flake or powdery
Graphite, or charcoal, borax, ice crystal can use one of which, can also by it is several mixed with arbitrary proportion after make
With.
Operated as follows：
1）Bi brass old material, heating fusing are added in smelting furnace；
2）Brass old material liquation is covered as coverture with graphite flake, the thickness of coverture is 50 millimeters；
3）Ready additive is added, addition is the 2.5% of brass old material weight, together melting, alloying, control
Smelting temperature is 1150 DEG C, melting 30 minutes；Uniform stirring promotes alloying process uniform in fusion process；
4）Sodium fluoride is added as cleaner, weight for brass old material weight 0.3%, insulation stand 20 minutes, through except
Gas, take off miscellaneous；
5）950 DEG C are cooled to, 1000 DEG C can be also cooled to, be cast into ingot casting.
It is 0.0218% that sampling analysis, which obtains bi content in ingot casting, and it is 97.2% to be computed drop bismuth rate.Table 3 is in embodiment
Technological parameter and drop bismuth effect.
| Bismuth additive drops | Cleaner | Smelting temperature | Smelting time | Time of repose | Bismuth rate drops |
| 2.5% | 0.3% | 1150℃ | 30min | 20min | 97.2% |
Table 3
Embodiment 4
This batch of brass old material bi content 0.68%.Additive preparation, using by the major ingredient that percentage by weight is 65%, weight hundred
Divide the additive for the second auxiliary material composition that ratio is 15% auxiliary material and percentage by weight is 20%.Cleaner selects sodium fluoride, can also
Mixed from calcirm-fluoride, or by sodium fluoride with calcirm-fluoride with arbitrary proportion.Coverture is from graphite flake or powdery
Graphite, or charcoal, borax, ice crystal, can use one of which, can also by it is several mixed with arbitrary proportion after use.
Operated as follows：
1）Bi brass old material, heating fusing are added in smelting furnace；
2）It is 1 with weight ratio:1 graphite flake and ice crystal mixing covers brass old material liquation, coverture as coverture
Thickness be 50 millimeters；
3）Ready additive is added, addition is the 2% of brass old material weight, together melting, alloying, control is molten
It is 1000 DEG C, melting 40 minutes to refine temperature；Uniform stirring promotes alloying process uniform in fusion process；
4）Sodium fluoride is added as cleaner, weight for brass old material weight 0.5%, insulation stand 10 minutes, through except
Gas, take off miscellaneous；
5）950 DEG C are cooled to, 1000 DEG C can be also cooled to, be cast into ingot casting.
It is 0.0453% that sampling analysis, which obtains bi content in sample, and it is 93.3% to be computed drop bismuth rate.Table 4 is in embodiment
Technological parameter and drop bismuth effect.
| Bismuth additive drops | Cleaner | Smelting temperature | Smelting time | Time of repose | Bismuth rate drops |
| 2.0% | 0.5% | 1000℃ | 40min | 10min | 93.3% |
Table 4
Embodiment 5
This batch of brass old material bi content 0.70%.Additive preparation, using by the major ingredient that percentage by weight is 70%, weight hundred
Divide the additive for the second auxiliary material composition that ratio is 10% auxiliary material and percentage by weight is 20%.Cleaner selects sodium fluoride, can also
Mixed from calcirm-fluoride, or by sodium fluoride with calcirm-fluoride with arbitrary proportion.Coverture is from graphite flake or powdery
Graphite, or charcoal, borax, ice crystal, can use one of which, can also by it is several mixed with arbitrary proportion after use.
Operated as follows：
1）Bi brass old material, heating fusing are added in smelting furnace；
2）It is 1 with weight ratio:1 graphite flake and borax mixing covers brass old material liquation as coverture, coverture
Thickness is 40 millimeters；
3）Ready additive is added, addition is the 3.5% of brass old material weight, together melting, alloying, control
Smelting temperature is 1100 DEG C, melting 35 minutes；Uniform stirring promotes alloying process uniform in fusion process；
4）Sodium fluoride is added as cleaner, weight for brass old material weight 0.4%, insulation stand 15 minutes, through except
Gas, take off miscellaneous；
5）950 DEG C are cooled to, 1000 DEG C can be also cooled to, sampling analysis is cast into ingot casting.
Bi content is 0.0259% in ingot casting, and it is 96.3% to be computed drop bismuth rate.Table 5 is the technological parameter and drop in embodiment
Bismuth effect.
| Bismuth additive drops | Cleaner | Smelting temperature | Smelting time | Time of repose | Bismuth rate drops |
| 3.5% | 0.4% | 1100℃ | 35min | 15min | 96.3% |
Table 5
A kind of method for reducing bi content in brass of the present invention, with advantages below：
Physical Metallurgy is combined by the present invention with Alloying Treatment brass alloys technology, is reclaimed for Bi brass with making profits again
With this method has except the characteristics of bismuth effect is good, technique is simple, processing cost is low, through the bismuth-brass alloy after the technical finesse
Material is used available for reproduction.
The present invention can be used for the recycling and regeneration of bismuth yellow brass waste material, be a kind of environment-friendly circulation warp
Ji processing method, it is possible to resolve existing Bi brass material processes problem, while the Bi brass after processing can be reapplied in machinery
Manufacture field, with significant economic benefit and social benefit.
Above-mentioned example is only intended to the explanation present invention, in addition, also a variety of different embodiments, and these are implemented
Mode be all those skilled in the art after comprehension inventive concept it is also envisioned that therefore, will not enumerate herein.
Unless otherwise indicated, all technical terms used herein are generally understood that with professional and technical personnel in the field
Implication is identical, and all technical terms used in text are simply to illustrate that the purpose of description specific embodiment, is not intended to
Limit the scope of the present invention.
Except there is a special instruction, in the present invention used various reagents, raw material be in the market purchase commodity or can be with
Pass through product made from the method informed.
Claims (8)
1. a kind of method for reducing bi content in brass, it is characterised in that comprise the following steps：
1）Bismuth yellow brass, heating fusing are added in smelting furnace；
2）And covered with coverture；
3）The additive of bi content in reduction bismuth yellow brass is added, the additive is made up of major ingredient, auxiliary material and the second auxiliary material；Institute
State major ingredient to be made up of a kind of intermediate compound or a variety of intermediate compounds in lithium, calcium, strontium, barium, major ingredient accounts for weight of additive hundred
Divide than being 60~70%；The auxiliary material is made up of one or more mixing in cerium, yttrium, the oxide of lanthanum, and auxiliary material accounts for addition
The percentage by weight of agent is 10~30%；Second auxiliary material one or more in Boratex, sodium chloride, sodium carbonate are constituted, the
The percentage by weight that two auxiliary materials account for additive is 10~20%, and addition is the 1.0~3.5% of the bismuth yellow brass weight, melting,
Alloying；
4）Cleaner is added, is incubated, stands, taking off miscellaneous；
5）Carry out alloy casting.
2. as claimed in claim 1 reduction brass in bi content method, it is characterised in that step 2) described in coverture be
One or more combinations in graphite, charcoal, borax, ice crystal, the thickness of coverture is 30~50 millimeters.
3. the method for bi content in brass is reduced as claimed in claim 1, it is characterised in that step 4）Described in cleaner be
Sodium fluoride or calcirm-fluoride, or sodium fluoride and calcirm-fluoride mixture.
4. the method for bi content in brass is reduced as claimed in claim 2, it is characterised in that step 3）Middle smelting temperature is
1000~1150 DEG C, smelting time is 30~40 minutes.
5. the method for bi content in brass is reduced as claimed in claim 1, it is characterised in that step 5）Middle cast temperature is not low
In 950 DEG C.
6. the method for bi content in brass is reduced as claimed in claim 5, it is characterised in that step 5）Middle cast temperature exists
Between 950~1050 DEG C.
7. the method for bi content in brass is reduced as claimed in claim 1, it is characterised in that step 4）Middle time of repose is 10
~20 minutes.
8. the method for bi content in brass is reduced as claimed in claim 1, it is characterised in that step 4）The addition of middle cleaner
Measure as the 0.1~0.5% of the bismuth yellow brass weight.
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| CN107058777A (en) * | 2017-04-18 | 2017-08-18 | 中南大学 | It is a kind of to remove Bi, Pb refining agent and preparation method thereof in waste and old Bi brass |
| CN111020265A (en) * | 2019-11-11 | 2020-04-17 | 宁波长振铜业有限公司 | Bismuth-removing additive for removing impurity element bismuth in regenerated brass and application thereof |
| CN113414359A (en) * | 2021-06-15 | 2021-09-21 | 宁波金田铜业(集团)股份有限公司 | Method for preparing oxygen-free copper by horizontal continuous casting |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103146939A (en) * | 2013-02-06 | 2013-06-12 | 江西理工大学 | Method for reducing content of lead in lead brass |
| CN104357699A (en) * | 2014-09-29 | 2015-02-18 | 苏州有色金属研究院有限公司 | Tin removal refining agent and use thereof |
| CN104894412A (en) * | 2015-04-16 | 2015-09-09 | 新疆大学 | Method for removing impurity during copper and copper alloy melting process |
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| JP2006274383A (en) * | 2005-03-30 | 2006-10-12 | Hitachi Cable Ltd | Method for manufacturing copper material, and copper material |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103146939A (en) * | 2013-02-06 | 2013-06-12 | 江西理工大学 | Method for reducing content of lead in lead brass |
| CN104357699A (en) * | 2014-09-29 | 2015-02-18 | 苏州有色金属研究院有限公司 | Tin removal refining agent and use thereof |
| CN104894412A (en) * | 2015-04-16 | 2015-09-09 | 新疆大学 | Method for removing impurity during copper and copper alloy melting process |
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