CN111020265A - Bismuth-removing additive for removing impurity element bismuth in regenerated brass and application thereof - Google Patents
Bismuth-removing additive for removing impurity element bismuth in regenerated brass and application thereof Download PDFInfo
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- CN111020265A CN111020265A CN201911095408.0A CN201911095408A CN111020265A CN 111020265 A CN111020265 A CN 111020265A CN 201911095408 A CN201911095408 A CN 201911095408A CN 111020265 A CN111020265 A CN 111020265A
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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
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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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
- C22C9/04—Alloys based on copper with zinc as the next major constituent
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Abstract
The invention belongs to the technical field of melt purification in a copper casting process, and particularly relates to a bismuth removing additive for removing impurity element bismuth in regenerated brass, which comprises 60-80% of calcium-zinc alloy, 10-20% of sodium fluoride and 10-20% of calcium fluoride in percentage by weight. The bismuth-containing regenerated brass is used as a main raw material, the temperature of a melt is reduced to 910-960 ℃ after the bismuth-containing regenerated brass is completely melted, the bismuth-removing additive is added, the temperature is kept for 15-20 minutes, so that a bismuth metal compound is formed, the melt is refined, discharged and cast at 1000-1040 ℃ through slag gathering and floating, and the bismuth-removed regenerated brass is obtained. The invention overcomes the defects that the recycled brass in the prior art has high bismuth content and brings great difficulty to the recycling of the recycled brass, and has the functions of effectively removing the impurity bismuth in the brass melt and improving the quality of the brass; meanwhile, the use method is simple, and the bismuth removing effect is extremely high on the premise of small addition amount.
Description
Technical Field
The invention belongs to the technical field of melt purification in a copper casting process, and particularly relates to a bismuth removing additive for removing impurity element bismuth in regenerated brass and application thereof.
Background
China is the biggest copper processing material producing country, trade country and consumer country in the world at present, but China is in shortage of copper resources, and the contradiction between raw material supply and consumption demand is increasingly prominent; the copper has good regeneration performance, and compared with the original copper, the regenerated copper has the advantages of energy conservation, environmental protection, economy and the like as a raw material, so the regenerated copper becomes an important raw material source of the copper industry. The industry of the reclaimed copper in China has been rapidly developed in recent years, and the yield of the reclaimed copper is rapidly increased. The main sources of the secondary copper are scrap copper-containing waste parts, waste materials in the production of copper, copper alloy and mechanical processing processes thereof, copper slag, smoke dust in the smelting process and the like. The recycled brass is one of the waste copper in large quantity, if the purchased raw materials are used for simply recovering copper, the grade of the copper is not high, and the zinc element is greatly wasted, so that the method for producing the brass alloy by directly utilizing the recycled brass raw materials is the most economical and feasible method.
The regenerated brass has wide raw material sources and complex components, wherein the lead brass has good cutting performance and low price advantage and is widely applied at home and abroad, but lead is a heavy metal which is extremely harmful to human bodies, and along with the continuous enhancement of environmental protection consciousness of people, the application of the lead-containing brass alloy is limited by environmental protection departments at home and abroad, particularly in developed countries, the limitation is stricter, and under the background, a part of lead brass is replaced by the lead-free-cutting brass alloy. The lead-free-cutting brass containing bismuth replaces lead brass most, and the market occupation is large. The recycled brass is inevitably recycled by using bismuth-containing brass waste. The bismuth content of the lead-free bismuth brass is generally higher than 0.8 wt%, the bismuth in the brass is more than 100ppm, the processing brittleness and even cracking of the copper alloy can be caused, and in the recycling of the regenerated waste brass, the bismuth brass is easily mixed with the common brass, so that great difficulty is brought to the recycling of the regenerated brass. Therefore, the research on the technology for removing the bismuth content in the raw material of the bismuth brass has great significance for the field of brass regeneration.
At present, a few patents on bismuth removal from melts developed in China exist, 106191503A discloses a method for reducing the content of bismuth in brass, main materials of an additive are lithium, calcium, strontium, barium and the like, auxiliary materials are rare earth oxides, second auxiliary materials are sodium borate, sodium chloride, sodium carbonate and the like, a compound can be formed with bismuth in brass at a high temperature, and the formed compound is removed from the melt as an impurity through a high-temperature metallurgy method, so that the purpose of reducing the content of bismuth in brass is achieved. CN107058777A discloses a refining agent for removing Bi and Pb in waste bismuth brass, which contains any one or more of La (lanthanum), Ce (cerium), Ti (titanium), Zr (zirconium), Y (yttrium), Ca (calcium), Mg (magnesium) or Nd (neodymium).
Disclosure of Invention
The invention provides a bismuth removing additive for removing impurity element bismuth in regenerated brass and a method for removing bismuth in regenerated brass by the additive, aiming at overcoming the defects that the content of bismuth in a brass regenerated raw material in the prior art is high and great difficulty is brought to the recycling of the regenerated brass.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the bismuth removing additive for removing the impurity element bismuth in the regenerated brass comprises, by weight, 60-80% of calcium-zinc alloy, 10-20% of sodium fluoride and 10-20% of calcium fluoride.
According to the chemical principle of the invention, Ca can react with Bi at high temperature to generate Ca3Bi2Compound, since its density is lower than that of brass (8.5 g/cm)3) Therefore, the floating of light metal compounds can be realized by utilizing the density difference; sodium fluoride and calcium fluoride are added because they can convert Ca produced3Bi2The compound is coagulated and gathered to slag, thereby being beneficial to fishing. Meanwhile, the sodium fluoride and the calcium fluoride can also reduce the viscosity of the slag, and the slag has the following two effects: (1) The floating of the slag is facilitated, so that the slag can be removed as far as possible; (2) after the viscosity is reduced, the amount of the brass melt which can be adhered to the surface of the slag is effectively reduced, and the waste of the brass is prevented.
Preferably, the mass percentage of the calcium element in the calcium-zinc alloy is 20-30%.
According to the invention, the calcium-zinc alloy is adopted as the main raw material of the bismuth removing additive, the calcium element participates in the reaction with the bismuth element, the zinc element is the main element in the brass, so that the introduction of new impurities can be avoided, and the problem of burning loss caused when the calcium element is added into a melt in a simple substance form is avoided, thereby improving the bismuth removing efficiency.
A method for removing impurity element bismuth in regenerated brass, which comprises the following steps:
(1) adding a bismuth-containing regenerated brass raw material into a smelting furnace, and completely smelting;
(2) adding the bismuth-removing additive into the melt, and stirring and mixing;
(3) after the bismuth-removing additive is melted, the mixture is subjected to heat preservation and deslagging, then the mixture is refined, and the refined mixture is taken out of the furnace and cast ingot to obtain the bismuth-removed regenerated brass.
The bismuth removing method is simple, only the bismuth removing additive is added into the bismuth-containing regenerated brass melt, calcium elements in calcium-zinc alloy in the additive can be combined with bismuth elements after the bismuth removing additive is uniformly stirred to form low-density slag, and only the bismuth-containing slag needs to be fished out in subsequent treatment, so that the bismuth content in the brass melt is effectively reduced, the quality of the brass alloy is improved, and the waste and the cost are reduced.
Preferably, the bismuth content in the bismuth-containing regenerated brass raw material is 0.5-3 wt%.
Preferably, the addition amount of the bismuth-removing additive is 0.5-2.5% of the mass of the bismuth-containing regenerated brass raw material.
The bismuth-removing additive is only 0.5-2.5% of the mass of the bismuth-containing regenerated brass raw material, has the characteristic of small addition amount, still has a good bismuth-removing effect on the premise of small addition amount, can greatly reduce the bismuth content in the brass by more than 99.7% after the refining agent is added, and basically achieves the effect of removing bismuth.
Preferably, in the step (2), the melt temperature is controlled to be 910-960 ℃ when the bismuth removing additive is added.
The reason why the temperature of the melt is controlled to be 910-960 ℃ is that the bismuth-containing compound generated by the reaction has certain solubility in the melt due to the excessively high temperature of the melt, so that slag is not easy to separate out, and meanwhile, the slag is not easy to gather due to the excessively high temperature, so that the slag salvage rate is low, and the effect is greatly reduced. However, if the melt temperature is low, the viscosity of the brass melt is high, so that the slag fished out in the slag fishing process can carry more brass, and the brass is wasted. Therefore, repeated tests show that when the temperature is in the range of 910-960 ℃, slag can be effectively salvaged, brass can be effectively reduced from being taken out, and brass waste is reduced.
Preferably, the bismuth removing additive in the step (2) is wrapped by copper foil during addition and is added to the lower middle part of the melt.
The bismuth-removing additive in the invention has lower density compared with brass melt, and if the bismuth-removing additive is directly added, the bismuth-removing additive floats on the surface of the melt, so that the bismuth element in the melt cannot be effectively removed. Therefore, the bismuth removing additive is wrapped by the copper foil and then added to the middle lower part of the melt, so that bismuth in the melt can be effectively and completely removed by reaction, and the bismuth removing efficiency is ensured.
Preferably, the bismuth-removing additive is added and stirred for 3-5 min.
Preferably, the heat preservation time in the step (3) is 15 to 20 minutes.
Preferably, after the heat preservation in the step (3) is finished, the temperature is raised to 1000-1040 ℃ for refining.
Therefore, the invention has the following beneficial effects:
(1) impurity bismuth in the brass melt can be effectively removed, and the quality of brass is improved;
(2) the using method is simple;
(3) has extremely high bismuth removing effect on the premise of small addition amount.
Detailed Description
The invention is further described with reference to specific examples. The following description of the embodiments is provided to enable any person skilled in the art to make and use the invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the following embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Example 1
The bismuth-removing additive comprises the following components: 60 wt% of calcium-zinc alloy, 20 wt% of sodium fluoride and 20 wt% of calcium fluoride, wherein the mass percentage of calcium element in the calcium-zinc alloy is 30 wt%.
| Additive agent | Bismuth-containing regenerated brass | Temperature of addition | Time of heat preservation | Refining temperature |
| 0.50％ | 100Kg | 960℃ | 15min | 1000℃ |
The method comprises the steps of pretreating a regenerated brass raw material, melting and sampling in a melting furnace, measuring the Bi content by straight smooth paving of 2.849%, adjusting the temperature of a melt to 960 ℃, adding an additive coated with a copper foil to the middle lower part of the melt, stirring for 5min, keeping the temperature for 15 min, heating to 1000 ℃, refining, sampling and analyzing, discharging the melt from the furnace, casting ingots, measuring by direct-reading spectroscopy, wherein the Bi content is 2.361%, and the comparison result shows that the Bi content is reduced by 0.488%.
Example 2
The bismuth-removing additive comprises the following components: 70 wt% of calcium-zinc alloy, 15 wt% of sodium fluoride and 15 wt% of calcium fluoride, wherein the mass percentage of calcium element in the calcium-zinc alloy is 25 wt%.
| Additive agent | Pretreated waste brass | Temperature of addition | Time of heat preservation | Refining temperature |
| 1.5％ | 100Kg | 945℃ | 17min | 1020℃ |
Pretreating the scrap copper raw material, melting and sampling in a smelting furnace, measuring the Pb content by straight light spreading to be 1.549%, adjusting the temperature of a melt to be 945 ℃, adding an additive coated with copper foil to the middle lower part of the melt, stirring for 3min, keeping the temperature for 14 min, then heating to 1010 ℃, refining, sampling and analyzing, discharging the melt from the furnace, casting ingot, measuring the Pb content by direct reading spectrum to be 0.049%, and calculating the comparison result to show that the bismuth content is reduced by 1.5%, and basically removing the bismuth element.
Example 3
The bismuth-removing additive comprises the following components: 68 wt% of calcium-zinc alloy, 14 wt% of sodium fluoride and 18 wt% of calcium fluoride, wherein the mass percentage of calcium element in the calcium-zinc alloy is 22 wt%.
| Additive agent | Pretreated waste brass and zinc block | Temperature of addition | Time of heat preservation | Refining temperature |
| 2.0％ | 100Kg | 930℃ | 18min | 1030℃ |
Pretreating the scrap copper raw material, melting and sampling in a melting furnace, measuring the Bi content by straight smooth paving to be 1.815%, adjusting the melt temperature to 930 ℃, adding an additive coated with copper foil to the middle lower part of the melt, stirring for 4min, preserving heat for 18 min, then heating to 1030 ℃, refining, sampling and analyzing, discharging from the furnace, casting ingot, measuring by direct reading spectrum, wherein the Bi content is 0.005%, and the comparison result shows that the Bi content is reduced by 1.81%, reaches 0.005%, and the bismuth element is basically removed.
Example 4
The bismuth-removing additive comprises the following components: 75 wt% of calcium-zinc alloy, 12 wt% of sodium fluoride and 13 wt% of calcium fluoride, wherein the mass percentage of calcium element in the calcium-zinc alloy is 20 wt%.
| Additive agent | Pretreated waste brass | Temperature of addition | Time of heat preservation | Refining temperature |
| 2.5％ | 100Kg | 915℃ | 19min | 1025℃ |
Pretreating the scrap copper raw material, melting and sampling in a smelting furnace, measuring the Bi content by straight smooth paving to be 2.232%, adjusting the temperature of the melt to 915 ℃, adding an additive coated with copper foil to the middle lower part of the melt, stirring for 5min, preserving the heat for 20 min, then heating to 1035 ℃, refining, sampling and analyzing, discharging the melt from the furnace, casting the ingot, measuring the Bi content by direct reading spectrum to be 0.004%, calculating the comparison result to show that the Bi content is reduced by 2.228%, the Bi content reaches 0.004%, and basically removing the bismuth element.
Example 5
The bismuth-removing additive comprises the following components: 80 wt% of calcium-zinc alloy, 10 wt% of sodium fluoride and 10 wt% of calcium fluoride, wherein the mass percentage of calcium element in the calcium-zinc alloy is 25 wt%.
| Additive agent | Pretreated waste brass and zinc block | Temperature of addition | Time of heat preservation | Refining temperature |
| 2.0％ | 100Kg | 960℃ | 16min | 1030℃ |
Pretreating the scrap copper raw material, melting and sampling in a melting furnace, measuring the Bi content by straight smooth paving to be 1.945%, adjusting the temperature of the melt to be 960 ℃, adding an additive coated with copper foil to the middle lower part of the melt, stirring for 4min, keeping the temperature for 18 min, then heating to 1040 ℃, refining, sampling and analyzing, discharging the melt from the furnace, casting ingot, measuring by direct reading spectrum, wherein the Bi content is 0.009%, and the comparison result shows that the Bi content is reduced by 1.936%, reaches 0.009%, and basically removes the bismuth element.
The above-described embodiment is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the scope of the invention as set forth in the claims.
Claims (9)
1. The bismuth-removing additive for removing impurity element bismuth in the regenerated brass is characterized by comprising, by weight, 60-80% of calcium-zinc alloy, 10-20% of sodium fluoride and 10-20% of calcium fluoride.
2. The bismuth removing additive for removing impurity element bismuth in the regenerated brass as claimed in claim 1, wherein the mass percentage of calcium element in the calcium-zinc alloy is 20-30%.
3. A method for removing impurity element bismuth in regenerated brass is characterized by comprising the following steps:
(1) adding a bismuth-containing regenerated brass raw material into a smelting furnace, and completely smelting;
(2) adding the bismuth-removing additive as defined in claim 1 or 2 to the melt, stirring and mixing;
(3) after the bismuth-removing additive is melted, the mixture is subjected to heat preservation and deslagging, then the mixture is refined, and the refined mixture is taken out of the furnace and cast ingot to obtain the bismuth-removed regenerated brass.
4. The method for removing impurity element bismuth in the regenerated brass as claimed in claim 3, wherein the addition amount of the bismuth-removing additive is 0.5-2.5% of the mass of the raw material of the bismuth-containing regenerated brass.
5. The method for removing impurity element bismuth in the regenerated brass as claimed in claim 4, wherein the step (2) controls the melt temperature to be 910-960 ℃ when the bismuth removing additive is added.
6. The method for removing impurity element bismuth in recycled brass as claimed in claim 3, 4 or 5, wherein said bismuth removing additive in step (2) is wrapped with copper foil and added to the lower part of the melt during the addition.
7. The method for removing impurity element bismuth in regenerated brass as claimed in claim 6, wherein the bismuth removing additive is added and stirred for 3-5 min.
8. The method for removing impurity element bismuth in the regenerated brass as claimed in claim 3, wherein the holding time in step (3) is 15-20 minutes.
9. The method for removing impurity element bismuth from regenerated brass according to claim 3 or 8, characterized in that the temperature is raised to 1000-1040 ℃ for refining after the heat preservation in step (3) is finished.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911095408.0A CN111020265A (en) | 2019-11-11 | 2019-11-11 | Bismuth-removing additive for removing impurity element bismuth in regenerated brass and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911095408.0A CN111020265A (en) | 2019-11-11 | 2019-11-11 | Bismuth-removing additive for removing impurity element bismuth in regenerated brass and application thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1987002070A1 (en) * | 1985-10-04 | 1987-04-09 | London & Scandinavian Metallurgical Co Limited | Grain refining of copper-based alloys |
| CN106191503A (en) * | 2016-08-30 | 2016-12-07 | 江西理工大学 | A kind of reduce the method for bi content in pyrite |
| 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 |
| CN109371248A (en) * | 2018-12-04 | 2019-02-22 | 宁波长振铜业有限公司 | A method of reducing lead content in waste and old brass |
-
2019
- 2019-11-11 CN CN201911095408.0A patent/CN111020265A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1987002070A1 (en) * | 1985-10-04 | 1987-04-09 | London & Scandinavian Metallurgical Co Limited | Grain refining of copper-based alloys |
| CN106191503A (en) * | 2016-08-30 | 2016-12-07 | 江西理工大学 | A kind of reduce the method for bi content in pyrite |
| 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 |
| CN109371248A (en) * | 2018-12-04 | 2019-02-22 | 宁波长振铜业有限公司 | A method of reducing lead content in waste and old brass |
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