CN105821235A - Intermediate alloy for deoxygenation and refining of impure red copper and application and preparation method of intermediate alloy - Google Patents
Intermediate alloy for deoxygenation and refining of impure red copper and application and preparation method of intermediate alloy Download PDFInfo
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- CN105821235A CN105821235A CN201610171635.7A CN201610171635A CN105821235A CN 105821235 A CN105821235 A CN 105821235A CN 201610171635 A CN201610171635 A CN 201610171635A CN 105821235 A CN105821235 A CN 105821235A
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- deoxygenation
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000010949 copper Substances 0.000 title claims abstract description 84
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 84
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 54
- 239000000956 alloy Substances 0.000 title claims abstract description 54
- 238000007670 refining Methods 0.000 title claims abstract description 30
- 238000006392 deoxygenation reaction Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 28
- 239000012535 impurity Substances 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims description 38
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 23
- 239000011575 calcium Substances 0.000 claims description 23
- 229910052791 calcium Inorganic materials 0.000 claims description 23
- 239000002994 raw material Substances 0.000 claims description 20
- ALKZAGKDWUSJED-UHFFFAOYSA-N dinuclear copper ion Chemical compound [Cu].[Cu] ALKZAGKDWUSJED-UHFFFAOYSA-N 0.000 claims description 19
- 239000000470 constituent Substances 0.000 claims description 14
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 229910001122 Mischmetal Inorganic materials 0.000 claims description 4
- 238000003723 Smelting Methods 0.000 claims description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical group [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- WMOHXRDWCVHXGS-UHFFFAOYSA-N [La].[Ce] Chemical compound [La].[Ce] WMOHXRDWCVHXGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 18
- 239000001257 hydrogen Substances 0.000 abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 15
- 230000007547 defect Effects 0.000 abstract description 11
- 150000002910 rare earth metals Chemical class 0.000 abstract description 11
- 239000013078 crystal Substances 0.000 abstract description 9
- 229910000881 Cu alloy Inorganic materials 0.000 abstract description 8
- 239000002893 slag Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 abstract 3
- 239000002245 particle Substances 0.000 abstract 1
- 238000005266 casting Methods 0.000 description 27
- 238000002844 melting Methods 0.000 description 16
- 230000008018 melting Effects 0.000 description 16
- -1 during casting Substances 0.000 description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 239000002142 lead-calcium alloy Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 238000009749 continuous casting Methods 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 238000007499 fusion processing Methods 0.000 description 5
- 239000010813 municipal solid waste Substances 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 4
- 229910052745 lead Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical group [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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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
-
- 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
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C24/00—Alloys based on an alkali or an alkaline earth metal
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
- C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
- C22C30/04—Alloys containing less than 50% by weight of each constituent containing tin or lead
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses intermediate alloy for deoxygenation and refining of impure red copper and an application and a preparation method of the intermediate alloy. The intermediate alloy for deoxygenation and refining of the impure red copper comprises, by mass percentage, 30-50wt% of a calcium element, 5-25wt% of a lead element, 0.3-0.5wt% of a rare earth element, 0-1wt% of an impurity element, and the balance a copper element. The intermediate alloy contains the calcium element, the lead element and the rare earth element. The calcium element not only has the deoxygenation effect, but also is an excellent modificator for copper alloy, crystal particles of a cast ingot can be refined, and accordingly electrical conductivity is improved. By means of lead atoms, the solubility of hydrogen in molten copper can be improved remarkably, the obtained cast ingot has good texture finally, generation of a large number of defects and bubbles is avoided, and the electrical conductivity of the cast ingot is enhanced. Impurities in the impure red copper are made into molten slag by means of the rare earth. Meanwhile, the proportions of all the elements are reasonable, so that the electrical conductivity of the cast ingot is high, and few bubbles and defects exist.
Description
Technical field
The present invention relates to recycled copper refining art, especially, relate to a kind of intermediate alloy for recycled copper deoxygenation refining.Moreover, it relates to a kind of application including the above-mentioned intermediate alloy for recycled copper deoxygenation refining and preparation method.
Background technology
Copper be apply in human history the earliest, widest metal material, it has good electric conductivity, corrosion resistance, nonmagnetic, the feature of low cost, is industrial important source material.Copper and alloy thereof, due to good combination property, are widely used in the various aspects of national economy, and fine copper is because having the electric conductivity of excellence, is widely used in electrically, electric power, telecommunication and electron trade.In fine copper, the content requirement of copper is higher, and the raw material therefore used during melting has new metal and recycled copper, when using recycled copper melting, though higher compared to the content of new metal oxygen and impurity element, there is the biggest cost advantage.
Temperature during recycled copper melting is 1150～1300 DEG C, including oxidation and two processes of reduction.In oxidizing process, along with the increase of Red copper oxide quantity in copper liquid, some impurity therein, such as aluminum, manganese, zinc, stannum, ferrum, arsenic, antimony and lead are by the order by itself and oxygen affinity size, the most oxidized, generating various oxide and enter slag, in addition, hydrogen and sulfur in copper liquid also can be removed.In reduction process, wash melt consumingly by gases such as steam insoluble in copper liquid a large amount of produced by chemical reaction, carbon monoxides, the most of gas in copper liquid is taken out of, simultaneously by Red copper oxide reduction.
In order to make the oxygen content in the ingot casting finally given relatively low, it is usually added into deoxidizer when recycled copper melting.Currently for copper and copper alloy, main deoxidizer is phosphorus.Phosphorus is the most frequently used deoxidizer, phosphorous reaches 0.1% mechanical performance that also will not reduce copper, but seriously damages the electric conductivity of copper.And in copper liquid, having following relation between hydrogen and oxygen: when the oxygen in copper liquid increases, the content of hydrogen will reduce；When the oxygen in copper liquid reduces, the content of hydrogen will increase.Although the copper liquid oxygen content processed through deoxidizer decreases, when hydrogen content adds, when hydrogen has exceeded the dissolubility in copper liquid, during casting, hydrogen can escape in gaseous form, so that ingot casting creates bubble and defect, even makes ingot casting ftracture time serious.
Summary of the invention
The invention provides a kind of intermediate alloy for recycled copper deoxygenation refining, to solve recycled copper melting, to obtain ingot casting electric conductivity low, there is the technical problem of bubble and defect.
The technical solution used in the present invention is as follows:
One aspect of the present invention provides a kind of intermediate alloy for recycled copper deoxygenation refining, includes by percentage to the quality: calcium constituent 30～50wt%, lead element 5～25wt%, rare earth element 0.3～0.5wt%, impurity element 0～1wt%, and surplus is copper.
Further, including by percentage to the quality: calcium constituent 50wt%, lead element 15wt%, rare earth element 0.5wt%, impurity element 0.5wt%, surplus is copper.
Further, described rare earth element is cerium, lanthanum or the mischmetal of rich cerium lanthanum.
Another aspect of the present invention provides the application of a kind of intermediate alloy for recycled copper deoxygenation refining, is put into recycled copper copper liquid with the 4 of recycled copper copper liquid weight～the ratio of 6% by above-mentioned intermediate alloy.
Further, after described intermediate alloy is crushed to 50～100mm, put into recycled copper copper liquid.
Present invention also offers the preparation method of a kind of intermediate alloy for recycled copper deoxygenation refining, comprise the following steps: by the mass percent of intermediate alloy, calcic raw material, raw material containing lead, rare earths material and copper-containing raw material smelting and pouring at 1080～1100 DEG C is formed intermediate alloy.
The method have the advantages that the intermediate alloy for recycled copper deoxygenation refining comprises calcium constituent, lead element and rare earth element.Calcium constituent is in addition to having deoxidation, or the alterant that copper alloy is good, the crystal grain of ingot casting can be made to refine, thus improve electric conductivity.Lead atom can be obviously improved hydrogen dissolubility in copper liquid, and the ingot structure obtained may finally be made preferable, it is to avoid produces substantial amounts of defect and bubble, strengthens the electric conductivity of ingot casting.Rare earth makes the impurity in recycled copper form slag.The most above-mentioned element uses rational proportioning to make ingot casting electric conductivity high, and bubble and defect are less.
In addition to objects, features and advantages described above, the present invention also has other objects, features and advantages.The present invention is further detailed explanation below.
Detailed description of the invention
Hereinafter embodiments of the invention are described in detail, but the multitude of different ways that the present invention can be defined by the claims and cover is implemented.
The preferred embodiments of the present invention provide a kind of intermediate alloy for recycled copper deoxygenation refining, including by percentage to the quality: calcium constituent 30～50wt%, lead element 5～25wt%, rare earth element 0.3～0.5wt%, impurity element 0～1wt%, surplus is copper.
In order to make the oxygen content in the ingot casting finally given relatively low, it is usually added into deoxidizer when recycled copper melting.When using calcium as deoxidizer, reduce in melt in addition to the effect of oxygen content except having, calcium or the good alterant of copper alloy, the crystal grain of ingot casting can be made to refine, thus improve electric conductivity.Owing to calcium is the most active metal, directly join with the form of new metal and copper melts there will be the security incidents such as blast, therefore should add with the form of intermediate alloy.
In copper liquid, having following relation: when the oxygen in copper liquid increases between hydrogen and oxygen, the content of hydrogen will reduce；When the oxygen in copper liquid reduces, the content of hydrogen will increase.Although the copper liquid oxygen content processed through deoxidizer decreases, when hydrogen content adds, when hydrogen has exceeded the dissolubility in copper liquid, during casting, hydrogen can escape in gaseous form, so that ingot casting creates bubble and defect, even makes ingot casting ftracture time serious.As Pb >=200ppm in copper liquid, Pb atom can instead of the Cu atom in lattice, owing to the volume ratio Cu atom of Pb atom is big, make lattice creates gap, H enters interstitial site, has been obviously improved hydrogen dissolubility in copper liquid, and the ingot structure obtained may finally be made preferable, will not produce substantial amounts of defect and bubble, electric conductivity is fine.Therefore, it can avoid the generation of bubble and defect by increasing the dissolubility of hydrogen.
The rare earth element impact on smelting copper alloy: (1) purifies and reduce the hazardness effect of harmful element in copper and copper alloy: 1. deoxidation；2. desulfidation；3. deoxidization desulfuration effect simultaneously；4. eliminate or reduce the illeffects of trace low-melting-point metal in metal material.(2) nonmetal inclusion go bad, remove and reduce its hazardness remaining in solid metallic.(3) microalloying of metal material or alloying.And the impurity of recycled copper copper liquid occurs absorption or complexing with rare earth ion, hence in slag former, form slag and be easy to separate, improve the purity of ingot casting.
Due to the purity problem of raw material or in technological operation, intermediate alloy there will be some impurity elements unavoidably, and for cost-effective consideration, can use the raw material containing certain impurity or intermediate alloy.When impurity element needs total amount to be less than 1%, impurity element does not affect the final action effect of intermediate alloy.
Above-mentioned intermediate alloy uses suitable ratio can ensure that recycled copper copper loss of thick fluid oxygen is thorough, gas content reduces, inclusion floating, ensure that casting continuously, semi-continuous casting or molding ingot casting field trash reduce, bubble is few, non-scale and fracture in follow-up deformation always, and the crystal grain refinement of ingot casting, dense structure, improves electric conductivity.
The method have the advantages that the intermediate alloy for recycled copper deoxygenation refining comprises calcium constituent, lead element and rare earth element.Calcium constituent is in addition to having deoxidation, or the alterant that copper alloy is good, the crystal grain of ingot casting can be made to refine, thus improve electric conductivity.Lead atom can be obviously improved hydrogen dissolubility in copper liquid, and the ingot structure obtained may finally be made preferable, it is to avoid produces substantial amounts of defect and bubble, strengthens the electric conductivity of ingot casting.Rare earth makes the impurity in recycled copper form slag.The most above-mentioned element uses rational proportioning to make ingot casting electric conductivity high, and bubble and defect are less.
Alternatively, including by percentage to the quality: calcium constituent 30wt%, lead element 15wt%, rare earth element 0.5wt%, impurity element 0.5wt%, surplus is copper.Alternatively, rare earth element is cerium, lanthanum or lanthanum or the mischmetal of rich cerium lanthanum.Rare earth element can be simple substance such as Ce elements, lanthanum element or be mixture, such as rich cerium and the mischmetal of lanthanum.
According to a further aspect in the invention, additionally provide the application of a kind of intermediate alloy for recycled copper deoxygenation refining, above-mentioned intermediate alloy is put into recycled copper copper liquid with the 3 of recycled copper copper liquid weight～the ratio of 4%.Adding with this ratio, the addition of intermediate alloy is relatively fewer, can ensure that calcium, lead, rare earth element content in recycled copper copper liquid is suitable simultaneously.It is preferably intermediate alloy to put into recycled copper copper liquid with the 4 of recycled copper copper liquid weight～the ratio of 6%.
Alternatively, after intermediate alloy is crushed to 50～100mm, put into recycled copper copper liquid.The intermediate alloy of this size, contact area is big, and response speed is fast, can react with recycled copper copper liquid fast and effectively.
The present invention also provides for the preparation method of a kind of intermediate alloy for recycled copper deoxygenation refining, comprises the following steps: by the mass percent of above-mentioned intermediate alloy, calcic raw material, raw material containing lead, rare earths material and copper-containing raw material smelting and pouring at 1080～1100 DEG C is formed intermediate alloy.Proportioning according to raw material, it is contemplated that the melting loss in each element fusion process carries out dispensing, then melting, pours into block intermediate alloy.For use copper-containing raw material can be elemental copper and copper alloy, calcic raw material can be electrolysis calcium, raw material containing lead can be simple substance lead and metal.
Embodiment 1
A kind of copper calcium lead alloy, wherein, according to mass percent, the constituent of this copper calcium lead alloy is: the content of calcium is 35%, and the content of lead is 20%, and the content of rare earth is 0.4%, and other inevitable impurity element total contents are less than 1%, and surplus is copper.Preparation method is: using copper, electrolysis calcium, lead and rare earth is raw material, it is contemplated that the melting loss in each element fusion process carries out dispensing, then melting in vaccum sensitive stove, pours into block intermediate alloy, is finally broken into 50～100mm.The copper calcium lead intermediate alloy block made is put in the copper liquid in flat refining furnace with the ratio of the 6% of recycled copper copper liquid weight, completes deoxygenation refining process.After semi-continuous casting or casting continuously, the ingot casting non-scale obtained and fracture, by structure observation, find that field trash reduces, bubble is few, and crystal grain is relatively fine.
Embodiment 2
A kind of copper calcium lead alloy, wherein, according to mass percent, the constituent of this copper calcium lead alloy is: the content of calcium is 30%, and the content of lead is 5%, and the content of rare earth is 0.3%, and other inevitable impurity element total contents are less than 0.1%, and surplus is copper.Preparation method is: using copper, electrolysis calcium, lead and rare earth is raw material, it is contemplated that the melting loss in each element fusion process carries out dispensing, then melting in vaccum sensitive stove, pours into block intermediate alloy, is finally broken into 50～100mm.In the copper liquid putting in flat refining furnace with the ratio of the 4% of recycled copper copper liquid weight by the copper calcium lead intermediate alloy block made, complete deoxygenation refining process.After semi-continuous casting, the ingot casting non-scale obtained and fracture, by structure observation, find that field trash reduces, bubble is few, and crystal grain is relatively fine.
Embodiment 3
A kind of copper calcium lead alloy, wherein, according to mass percent, the constituent of this copper calcium lead alloy is: the content of calcium is 50%, and the content of lead is 25%, and the content of rare earth is 0.5%, and other inevitable impurity element total contents are less than 1%, and surplus is copper.Preparation method is: using copper, electrolysis calcium, lead and rare earth is raw material, it is contemplated that the melting loss in each element fusion process carries out dispensing, then melting in vaccum sensitive stove, pours into block intermediate alloy, is finally broken into 50～100mm.In the copper liquid putting in flat refining furnace with the ratio of the 5% of recycled copper copper liquid weight by the copper calcium lead intermediate alloy block made, complete deoxygenation refining process.After semi-continuous casting or casting continuously, the ingot casting non-scale obtained and fracture, by structure observation, find that field trash reduces, bubble is few, and crystal grain is relatively fine.
Embodiment 4
A kind of copper calcium lead alloy, wherein, according to mass percent, the constituent of this copper calcium lead alloy is: the content of calcium is 50%, and the content of lead is 15%, and the content of rare earth is 0.5%, and other inevitable impurity element total contents are less than 5%, and surplus is copper.Preparation method is: using copper, electrolysis calcium, lead and rare earth is raw material, it is contemplated that the melting loss in each element fusion process carries out dispensing, then melting in vaccum sensitive stove, pours into block intermediate alloy, is finally broken into 50～100mm.In the copper liquid putting in flat refining furnace with the ratio of the 5% of recycled copper copper liquid weight by the copper calcium lead intermediate alloy block made, complete deoxygenation refining process.After semi-continuous casting or casting continuously, the ingot casting non-scale obtained and fracture, by structure observation, find that field trash reduces, bubble is few, and crystal grain is relatively fine.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.All within the spirit and principles in the present invention, any modification, equivalent substitution and improvement etc. made, should be included within the scope of the present invention.
Claims (6)
1. the intermediate alloy for recycled copper deoxygenation refining, it is characterised in that including by percentage to the quality: calcium constituent 30～50wt%, lead element 5～25wt%, rare earth element 0.3～0.5wt%, impurity element 0～1wt%, surplus is copper.
Intermediate alloy for recycled copper deoxygenation refining the most according to claim 1, it is characterised in that include by percentage to the quality: calcium constituent 50wt%, lead element 15wt%, rare earth element 0.5wt%, impurity element 0.5wt%, surplus is copper.
Intermediate alloy for recycled copper deoxygenation refining the most according to claim 1, it is characterised in that described rare earth element is cerium, lanthanum or the mischmetal of rich cerium lanthanum.
4. the application for the intermediate alloy of recycled copper deoxygenation refining, it is characterised in that the intermediate alloy any one of claims 1 to 3 is put into recycled copper copper liquid with the 4 of recycled copper copper liquid weight～the ratio of 6%.
The application of the intermediate alloy for recycled copper deoxygenation refining the most according to claim 4, it is characterised in that after described intermediate alloy is crushed to 50～100mm, puts into recycled copper copper liquid.
6. the preparation method for the intermediate alloy of recycled copper deoxygenation refining, it is characterized in that, comprise the following steps: by the mass percent of intermediate alloy, calcic raw material, raw material containing lead, rare earths material and copper-containing raw material smelting and pouring at 1080～1100 DEG C is formed intermediate alloy.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610171635.7A CN105821235B (en) | 2016-03-24 | 2016-03-24 | Intermediate alloy for recycled copper deoxygenation refining, using and preparation method |
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| CN201610171635.7A CN105821235B (en) | 2016-03-24 | 2016-03-24 | Intermediate alloy for recycled copper deoxygenation refining, using and preparation method |
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| Publication Number | Publication Date |
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| CN105821235A true CN105821235A (en) | 2016-08-03 |
| CN105821235B CN105821235B (en) | 2017-08-22 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108220645A (en) * | 2017-12-06 | 2018-06-29 | 常州杰轩纺织科技有限公司 | A kind of composite liquefied refining agent of recycled copper |
| CN111187917A (en) * | 2020-02-26 | 2020-05-22 | 烟台大学 | Removing agent and removing method for low-content impurity element tin in copper melt |
| CN113481394A (en) * | 2021-06-24 | 2021-10-08 | 宁波金田铜业(集团)股份有限公司 | Copper-iron alloy modifier, preparation method and use method thereof |
| CN113930639A (en) * | 2021-10-20 | 2022-01-14 | 江西金叶大铜科技有限公司 | Copper-calcium-rare earth alloy for refining red impure copper and removing impurities, and preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108220645A (en) * | 2017-12-06 | 2018-06-29 | 常州杰轩纺织科技有限公司 | A kind of composite liquefied refining agent of recycled copper |
| CN111187917A (en) * | 2020-02-26 | 2020-05-22 | 烟台大学 | Removing agent and removing method for low-content impurity element tin in copper melt |
| CN111187917B (en) * | 2020-02-26 | 2021-09-14 | 烟台大学 | Removing agent and removing method for low-content impurity element tin in copper melt |
| CN113481394A (en) * | 2021-06-24 | 2021-10-08 | 宁波金田铜业(集团)股份有限公司 | Copper-iron alloy modifier, preparation method and use method thereof |
| CN113930639A (en) * | 2021-10-20 | 2022-01-14 | 江西金叶大铜科技有限公司 | Copper-calcium-rare earth alloy for refining red impure copper and removing impurities, and preparation method and application thereof |
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| CN105821235B (en) | 2017-08-22 |
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Denomination of invention: Intermediate alloy for deoxygenation and refining of impure red copper and application and preparation method of intermediate alloy Effective date of registration: 20171221 Granted publication date: 20170822 Pledgee: Hunan Miluo rural commercial bank Limited by Share Ltd Pledgor: Hunan Yinlian Xiangbei Copper Industry Co., Ltd. Registration number: 2017430000111 |
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Effective date of registration: 20190104 Address after: 621000 No. 1 Sanjiang Road, Youxian Economic Development Zone, Mianyang City, Sichuan Province Patentee after: Mianyang Tongxin Copper Industry Co., Ltd. Address before: 414400 Miluo Industrial Park, Yueyang City, Hunan Province (west side of 107 National Highway New City Bridge) Patentee before: Hunan Yinlian Xiangbei Copper Industry Co., Ltd. |
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Effective date of registration: 20190424 Address after: 414400 Miluo Industrial Park, Yueyang City, Hunan Province (west side of 107 National Highway New City Bridge) Patentee after: Hunan Yinlian Xiangbei Copper Industry Co., Ltd. Address before: 621000 No. 1 Sanjiang Road, Youxian Economic Development Zone, Mianyang City, Sichuan Province Patentee before: Mianyang Tongxin Copper Industry Co., Ltd. |
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