CN1566379A - Copper-zinc separation method during smelting in a blast furnace - Google Patents
Copper-zinc separation method during smelting in a blast furnace Download PDFInfo
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- CN1566379A CN1566379A CN 03129568 CN03129568A CN1566379A CN 1566379 A CN1566379 A CN 1566379A CN 03129568 CN03129568 CN 03129568 CN 03129568 A CN03129568 A CN 03129568A CN 1566379 A CN1566379 A CN 1566379A
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- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000003723 Smelting Methods 0.000 title claims abstract description 34
- 238000000926 separation method Methods 0.000 title claims abstract description 20
- 239000010949 copper Substances 0.000 claims abstract description 81
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 73
- 229910052802 copper Inorganic materials 0.000 claims abstract description 66
- 239000011701 zinc Substances 0.000 claims abstract description 61
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 55
- 239000000463 material Substances 0.000 claims abstract description 46
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 37
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002893 slag Substances 0.000 claims abstract description 29
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 21
- 239000011787 zinc oxide Substances 0.000 claims abstract description 18
- 239000011593 sulfur Substances 0.000 claims abstract description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 8
- 238000005245 sintering Methods 0.000 claims abstract description 7
- 239000000428 dust Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 32
- 229910052787 antimony Inorganic materials 0.000 claims description 17
- 229910052785 arsenic Inorganic materials 0.000 claims description 17
- 235000019738 Limestone Nutrition 0.000 claims description 16
- 239000006028 limestone Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 229910052745 lead Inorganic materials 0.000 claims description 13
- 230000009467 reduction Effects 0.000 claims description 13
- 239000000571 coke Substances 0.000 claims description 12
- 229910052718 tin Inorganic materials 0.000 claims description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 11
- 229910052797 bismuth Inorganic materials 0.000 claims description 9
- 239000003546 flue gas Substances 0.000 claims description 8
- 239000004484 Briquette Substances 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims description 4
- 239000003830 anthracite Substances 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 4
- 238000002386 leaching Methods 0.000 claims description 4
- 239000002006 petroleum coke Substances 0.000 claims description 4
- 238000005987 sulfurization reaction Methods 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 239000011343 solid material Substances 0.000 claims description 2
- 229910017518 Cu Zn Inorganic materials 0.000 claims 3
- 229910017752 Cu-Zn Inorganic materials 0.000 claims 3
- 229910017943 Cu—Zn Inorganic materials 0.000 claims 3
- 238000007599 discharging Methods 0.000 claims 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 238000005204 segregation Methods 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 19
- 239000002184 metal Substances 0.000 description 19
- 238000006722 reduction reaction Methods 0.000 description 12
- 239000000126 substance Substances 0.000 description 10
- 238000011084 recovery Methods 0.000 description 9
- 239000012141 concentrate Substances 0.000 description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 229910052793 cadmium Inorganic materials 0.000 description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000005751 Copper oxide Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000024121 nodulation Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention disclose a copper-zinc separation method during smelting in a blast furnace which comprises, subjecting copper-zinc material to sintering, obtaining agglomerates whose sulfur content is less than 1.5%, proportioning lime carbonate and carbonaceous reducing agent by the ratio of 100% : 15-20% : 18-25%, loading the furnace charge into blast furnace, oxidizing the zinc into zinc oxide and loading into dust collector for reclamation, furnace hearth located at the furnace base storing crude copper, ice copper and slag, the ice copper and slag flowing into forehearth for segregation.
Description
Technical Field
The invention relates to the technical field of non-ferrous metal smelting, in particular to a smelting technology of a complex material of unmanageable multi-metal, which belongs to the technical field of a metallurgy method of a copper-zinc material.
Background
In the aspect of copper smelting, the fire method copper smelting which is still the dominating place until now is mainly the matte smelting method or the traditional converter blowing process, and the concentrate is mainly high-sulfur copper concentrate with the sulfur content of more than 28% and the sulfur-copper ratio of more than 1: 1. The zinc content of the material is strictly limited. Because zinc sulfide is oxidized and enters slag for slagging, the improvement of zinc grade in the slag can seriously affect the phenomena of slag viscosity, flue nodulation and the like, the normal production is affected, the limit is generally lower than 4 percent, and the content of some sealed blast furnaces and the like is controlled to be lower than 2 percent, so that the separation of copper and zinc in the traditional copper smelting method is impossible.
In the pyrometallurgical copper smelting, the production of copper in the reduction smelting production of blister copper is still very small, and the copper content in the production of secondary copper such as hypobrass, inferior purple impure copper and the like is dominant, so that the production of blister copper from copper oxide ore, low-sulfur copper concentrate, copper zinc concentrate or copper zinc slag is much less.
The separation flotation process is adopted for copper oxide in the Guangdong stone copper-recording ore in China to generate separated copper concentrate which does not contain sulfur, the concentrate is subjected to reduction smelting in a reverberatory furnace to directly produce blister copper, the annual output is 2 ten thousand tons, and the production history is 30 years.
In the 70 s, Amaks company, USA, utilized high-sulfur copper concentrate, firstly, full-oxidation roasting was carried out in a boiling smelting furnace, sulfuric acid was produced from high-concentration sulfur dioxide flue gas, roasted sand containing less than 1.5% of sulfur was agglomerated, the agglomerated product was reduced in a short blast furnace to obtain blister copper, slag flowed into an electric furnace, coke powder was added to continue reduction to produce black copper and waste slag, and the black copper was returned to a blast furnace as a reducing agent, and the method was produced in the company for many years. According to the records, the grade of crude copper discharged from the Amarsx method blast furnace is 98%, but the copper content of the slag is higher and is more than 1%, so that the blast furnace is operated by adopting a weaker reducing atmosphere, the smelting raw material is high-sulfur copper concentrate, the content of arsenic, lead, antimony and bismuth impurities is low generally, the slag produced by the blast furnace is further and deeply reduced by an electric furnace, and black copper containing 70% of copper and waste slag containing 0.5% of copper are produced.
The blast furnace smelting of secondary copper such as secondary brass and secondary red copper is different from the smelting of primary minerals or copper-zinc slag materials in the mechanism that most of copper and zinc exist in a metal form, only crude copper is melted in the smelting process, or zinc is volatilized into a steam state and enters flue gas, zinc oxide is easily obtained, and the separation of the copper and the zinc exists in a sulfide or oxide form and can be realized only in a stronger reducing atmosphere.
In the aspect of zinc smelting, the LS.P method of the British empire smelting company can be used forobtaining lead and zinc by smelting in a blast furnace to obtain crude lead and GOB zinc, but no technical report of copper and zinc separation process obtained by smelting in the blast furnace exists at home and abroad.
Disclosure of Invention
The invention aims to solve the technical problem of providing a copper-zinc separation method for blast furnace smelting of copper-zinc materials, which aims at the prior background art, utilizes different reduction sequences of oxides such as copper, zinc, iron and the like in the materials, utilizes a reducing agent to smelt in a copper-zinc blast furnace, correspondingly adjusts the slag type and controls the reduction degree, achieves the purpose of copper-zinc separation by one-time smelting, and has the characteristics of simple process, low investment, thorough separation, good comprehensive utilization of various valuable metal components in the materials, high metal recovery rate, low recovery cost, good economic benefit and the like, and opens up a new way for effectively treating the complex copper-zinc materials.
The technical scheme adopted by the invention for solving the technical problems is as follows: a blast furnace smelting copper-zinc separation method of copper-zinc material is characterized by that the copper-zinc material containing Cu 10-50%, Zn 5-40%, S5-15% and arsenic, lead, antimony and bismuth whose impurity contents are up to the requirements is firstly sintered to produce sintered block containing sulfur less than 1.5% or roasted briquetting method to obtain briquette containing sulfur less than 1.5%, then the briquette is mixed with limestone and carbon-containing reducing agent according to the mixing ratio of 100% to 15-20% to 18-25%, then these charging materials are fed into special blast furnace in batches and layers, the lower tuyereof blast furnace is blown with preheated air to make smelting, the top of furnace is equipped with secondary tuyere to blow secondary air, and the carbon monoxide and zinc vapour in the furnace gas are combusted to give out large quantity of heat quantity, and the furnace top is kept at high temp. above 1000 deg.C, so that the zinc oxide formed by oxidation is fed into dust collector and recovered with flue gas, the bottom cylinder of blast furnace is stored with raw copper, zinc, and zinc, The matte and the slag are discharged periodically, the blister copper and the slag continuously flow into a front bed for separation, the matte is returned for sintering, and the slag is quenched by water, if not specifically stated, the mass percentage is generally used in the text.
The chemical composition of the copper-zinc material is 10-50% of Cu, 5-40% of Zn, 5-15% of S, less than 0.5% of As, less than 0.5% of Pb, less than 0.5% of Sb, less than 0.5% of Sn and less than 0.4% of Bi.
The chemical components of the sintered block or the agglomerate are 10 to 55 percent of Cu, 5 to 45 percent of Zn, less than 1.5 percent of S, less than 0.4 percent of As, less than 0.5 percent of Pb, less than 0.4 percent of Sb, less than 0.5 percent of Sn and less than 0.4 percent of Bi, and the block diameter of the sintered block or the agglomerate is preferably controlled to be 30 to 120 mm.
The limestone contains CaO more than 50 percent, and the block diameter is preferably 30-80 mm.
The carbonaceous reducing agent is metallurgical coke, anthracite or petroleum coke, the content of C is more than 80 percent, and the block diameter is preferably 30-80 mm.
The copper-zinc blast furnace adopts a short material blast furnace and adopts double-bell charging, the height of a charging column is kept between 1.8 and 2.2 meters, a new batch of materials is charged to keep a specified height along with the reduction of the charging column, and the copper-zinc blast furnace is further characterized in that the furnace top is a high-temperature sealed furnace top, the necessary condition of keeping the temperature above 1000 ℃ is kept, secondary air is blown into the upper part of a material layer of the furnace top to oxidize zinc steam and carbon monoxide in furnace gas and generate a large amount of heat, so that the temperature of the furnace top reaches above 1000 ℃, and the normal reduction of furnace materials and the discharge of zinc oxide are kept. Introducing the high-temperature flue gas into a vaporization cooling flue and an air heat exchanger, preheating air used by a blast furnace to 300 ℃, cooling the flue gas containing zinc oxide by a surface cooler, and recovering a zinc oxide product by using a bag type dust collector. The tuyere of the blast furnace is rectangular in section, hot air at 300 ℃ is blown into the tuyere of the blast furnace for smelting according to a single row of air outlets on water jackets at two sides so as to strengthen the reduction reaction of the zinc oxide and save the consumption of metallurgical coke.
Reacting the following chemical reactions at high temperature in a blast furnace:
in the blast furnace, CuO in the sintered cake is firstly reduced into metallic copper, and then ZnO is reduced into metallic zinc, and the metallic copper rises with flue gas under the steam state at high temperature. Under the condition of the reducing atmosphere, part of iron oxide which is inevitable in local areas is reduced into metallic iron, but the zinc oxide is quickly replaced by the zinc oxide and is oxidized into the iron oxide again, and the iron oxide enters slag for slagging. Thus, the reduction of copper oxide into blister copper and the reduction of zinc oxide into zinc vapor are ensured in the furnace, and the zinc vapor rises to the top of the furnace and is oxidized into zinc oxide when encountering secondary air.
Because a small amount of sulfur is left in the sintered blocks or agglomerates, a small amount of copper matte is generated in the process, the amount of the copper matte is not more than 2 percent of the amount of the sintered blocks, three products are stored in the hearth, three layers are formed according to different specific gravities, the bottom of the hearth is provided with crude copper, the crude copper is discharged discontinuously in a siphon discharge mode, ingot casting crude copper blocks are used for anode refining, the copper matte and furnace slag continuously flow into a front bed from an outlet at the other end for further precipitation and separation, the furnace slag is discharged continuously for water quenching, and the copper matte is discharged discontinuously and returns to sintering.
The key technical problem of the invention is to maintain the high temperature of the tuyere zone of the blast furnace so that the zinc oxide can be easily reduced, wherein the high temperature is achieved by using a high-melting-point slag method, limestone is used as a fusing agent to be mixed in so that the slag alkalinity (CaO + MgO)/SiO2The proportion is 0.8-1.2, and the melting point of the slag is above 1050 ℃. The slag alkalinity of the blast furnace varies with the components of the materials to be treated, if the zinc content in the materials is low, the alkalinity should be reduced, and conversely, if the zinc content is high, the alkalinity should be properly increased.
Another technical key problem of the invention is to control the reducing atmosphere of the blast furnace, and the furnace gas component CO/CO before the secondary air at the top of the blast furnace is blown into the blast furnace2Is 1.0-1.2, and is controlled by adjusting the coke rate and the blast volume. The reducing atmosphere of the blast furnace also varies with the material properties, and if the zinc content in the burden is higher, the stronger the reducing atmosphere, CO/CO2The larger the value, the lower the zinc content, the opposite.
If the material treated by the method contains impurities such as arsenic, lead, antimony, bismuth and the like, the oxides of the material are easier to reduce into metal than zinc oxide, and simultaneously the oxides and copper form an alloy phase, so that the further refining of the crude copper is difficult. Therefore, the impurity content of the material processed by the method is required to be less than 0.5 percent of As, less than 0.5 percent of Pb, less than 0.5 percent of Sb, less than 0.5 percent of Sn and less than 0.4 percent of Bi. The copper and zinc materials which exceed the standard must be pretreated, and are subjected to smelting by the method after impurities are removed. The pretreatment can adopt an impregnation method, the concentration of sodium hydroxide solution is 80-160 g/L, the mass ratio of the sodium hydroxide solution to solid materials is 3-7: 1, the leaching time is 0.5-2 hours, the leaching temperature is 80-95 ℃, or adopt a sulfuration reduction roasting volatilization dearsenification method, the copper zinc material 36-58%, low-sulfur vulcanizing agent copper blue ore 36-58% and carbonaceous material 2-10% are crushed and uniformly mixed, particles with the diameter of 3-6mm are prepared by humidifying with water, then sulfuration reduction roasting is carried out in a rotary kiln for 1.5-2.5 hours at the temperature of 700-900 ℃, the concrete implementation method can refer to the patent already filed by the inventor, the patent application numbers are 02110571.5 and 02110552.9 respectively, in order to save the space, it will not be described again in the expanded state.
For copper-zinc materials containing 10-50% of Cu, 5-40% of Zn and 5-15% of S, the technical and economic indexes of copper-zinc separation smelting are as follows:
the furnace burden proportion is as follows:
sintered block (or agglomerate) 100%
Limestone (for sintered block) 10-20%
18-22% of metallurgical coke (for sintered block)
Blast furnace front bed energy rate of 50 ton/m2Day of the day
The crude copper contains Cu 92-96% and Zn 4-5%
90-95% of zinc oxide ZnO
The slag contains 0.6 percent of Cu
Consumption of main material (for one ton of copper metal)
0.5-0.9 ton of metallurgical coke
0.2-0.8 ton of limestone
And (3) metal recovery rate:
96 to 97 percent of copper
60 to 94 percent of zinc
90 percent of cadmium
In summary, compared with the prior art, the method has the advantages of simple process flow, thorough copper and zinc separation, good comprehensive utilization of multiple metal components, high metal recovery rate, low recovery cost, good economic benefit and the like, and opens up a new way for smelting complex metal ores.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
The adopted copper-zinc material is a high-zinc-copper material, and comprises the following chemical components: 25% of Cu, 40% of Zn, 10% of S, and the contents of As, Pb, Sb, Cd and Sn which are all below 0.5%, and sintering to obtain a sintered block, wherein the sintered block comprises the following chemical components: cu 28%, Zn 45%, S less than 1.5%, As 0.4%, Pb 0.4%, Sb 0.4%, Sn 0.4%, and copper-zinc separation and new smelting, thereby obtaining economic indexes:
the furnace burden proportion is as follows:
sintered block (or agglomerate) 100%
Limestone (for agglomerates) 20%
Metallurgical coke (for agglomerates) 25%
Blast furnace front bed energy rate of 50 ton/m2Day of the day
The blister copper contains Cu 94% and Zn 5%
ZnO 95% CdO 1.5%
Slag Cu 0.6% Zn 3-5%
(CaO+MgO)/SiO21.2
CO/CO21.2
Consumption of main material (for one ton of copper metal)
Metallurgical coke 0.9 ton
Limestone 0.8 ton
And (3) metal recovery rate:
97% of copper
92 percent of zinc
Example 2
The adopted copper-zinc material is a copper-zinc material with medium zinc content, and comprises the following chemical components: 25% of Cu, 25% of Zn, 78% of S6%, and the contents of As, Pb, Sb, Cd and Sn are all less than 0.5%, and sintering is carried out to obtain a sintered block, wherein the sintered block comprises the following chemical components: 28 percent of Cu, 28 percent of Zn, less than 1.5 percent of S, 0.4 percent of As, 0.4 percent of Pb, 0.4 percent of Sb, 0.4 percent of Sn, and the copper and zinc are separated and newly smelted to obtain economic indexes:
the furnace burden proportion is as follows:
sintered block (or agglomerate) 100%
Limestone (for agglomerates) 18%
Metallurgical coke (for agglomerates) 21%
Blast furnace front bed energy rate of 50 ton/m2Day of the day
The blister copper contains Cu 95% and Zn 3%
Slag Cu 0.6% Zn 3%
(CaO+MgO)/SiO21.0
CO/CO21.1
Consumption of main material (for one ton of copper metal)
Metallurgical coke 0.7 ton
Limestone 0.6 ton
And (3) metal recovery rate:
97% of copper
88 percent of zinc
Example 3
The adopted copper-zinc material is a copper-zinc material with low zinc content, and comprises the following chemical components: 25% of Cu,5% of Zn, 10% of S, and the contents of As, Pb, Sb, Cd and Sn which are all below 0.5%, and sintering to obtain a sintered block, wherein the sintered block comprises the following chemical components: 28 percent of Cu, 6 percent of Zn, less than 1.5 percent of S, 0.4 percent of As, 0.4 percent of Pb, 0.4 percent of Sb, 0.4 percent of Sn, and the copper and zinc are separated and newly smelted to obtain economic indexes:
the furnace burden proportion is as follows:
sintered block (or agglomerate) 100%
Limestone (for agglomerates) 15%
Metallurgical coke (for agglomerates) 18%
Blast furnace front bed energy rate of 50 ton/m2Day of the day
The blister copper contains Cu 96% and Zn 1%
Slag Cu 0.6% Zn 2%
(CaO+MgO)/SiO20.8
CO/CO21.0
Consumption of main material (for one ton of copper metal)
Metallurgical coke 0.5 ton
Limestone 0.4 ton
And (3) metal recovery rate:
97% of copper
60 percent of zinc
Example 4
The adopted copper-zinc material is a copper-zinc material with medium zinc content, and comprises the following chemical components: 25% of Cu, 25% of Zn, 6% of S, and the contents of As, Pb, Sb, Cd and Sn which are all less than 0.5%, and roasting to obtain a briquette, wherein the briquette comprises the following chemical components: 27 percent of Cu, 28 percent of Zn, less than 1.5 percent of S, 0.4 percent of As, 0.4 percent of Pb, 0.4 percent of Sb, 0.4 percent of Sn, and the copper and zinc are separated and newly smelted to obtain economic indexes:
the furnace burden proportion is as follows:
100 percent of lumps
Limestone (for agglomerates) 18%
Petroleum coke or anthracite (for briquettes) 21%
Blast furnace front bed energy rate of 51 ton/m2Day of the day
The blister copper contains Cu 93% and Zn 3%
Slag Cu 0.6% Zn 3%
(CaO+MgO)/SiO21.0
CO/CO21.1
Consumption of main material (for one ton of copper metal)
Petroleum coke or anthracite 0.7 ton
Limestone 0.6 ton
And (3) metal recovery rate:
copper content is 96%
87 percent of zinc
Claims (10)
1. A blast furnace smelting copper-zinc separation method of copper-zinc material is characterized by that the copper-zinc material containing Cu 10-50%, Zn 5-40%, S5-15% and arsenic, lead, antimony and bismuth whose impurity contents meet the requirements is firstly sintered to produce sintered block containing sulfur less than 1.5% or roasted briquetting method to obtain briquette containing sulfur less than 1.5%, then the briquette is mixed with limestone and carbon-containing reducing agent according to the mixing ratio of 100% to 15-20% to 18-25%, then the above-mentioned furnace materials are fed into the top of special blast furnace in batches and layers, and the lower tuyere of blast furnace is blown with preheated air to make smelting, and the top of furnace is equipped with secondary tuyere into which secondary air is blown, and the carbon monoxide and zinc vapour in the furnace gas are combusted to give out large quantity of heat quantity to keep high temp. over 1000 deg.C, so that the zinc oxide formed by oxidation can be fed into dust collector along with flue gas to recover, and the bottom cylinder of blast furnace is stored with raw copper, And discharging matte and slag, wherein the blister copper is discharged into an ingot at regular intervals, the matte and the slag continuously flow into a front bed for separation, the matte is returned for sintering, and the slag is quenched by water, wherein the percentage is mass percent.
2. The method of claim 1, wherein the Cu-Zn material comprises Cu 10-50%, Zn 5-40%, S5-15%, As<0.5%, Pb<0.5%, Sb<0.5%, Sn<0.5%, and Bi<0.4%.
3. The method according to claim 1, wherein said agglomerates or briquettes are comprised of Cu 10-55%, Zn 5-45%, S<1.5%, As<0.4%, Pb<0.5%, Sb<0.4%, Sn<0.5%, and Bi<0.4%.
4. The blast furnace smelting copper-zinc separation process according to claim 3, wherein said agglomerates or briquettes have a briquette diameter of 30-120 mm.
5. The method as claimed in claim 1, wherein said limestone contains CaO>50% and has a lump diameter of 30-80 mm.
6. The method of claim 1, wherein the carbonaceous reducing agent is metallurgical coke, anthracite or petroleum coke, contains C more than 80%, and has a block diameter of 30-80 mm.
7. Themethod of claim 1, wherein said limestone adjusts the basicity of the slag to (CaO + MgO)/SiO2The proportion is 0.8-1.2, and the melting point of the slag is ensured to be higher than 1050 ℃.
8. The method of claim 1, wherein the carbonaceous reductant is added in combination with adjusting the air-to-feed ratio to maintain the top flue gas CO/CO before the secondary air is blown2Is 1.0-1.2, and normal reducing atmosphere is maintained.
9. The method of claim 1, wherein the blast furnace is a short-column blast furnace, the blast furnace is charged by using a double-bell charging method, the height of the column is maintained at 1.8-2.2 m, the furnace top is sealed at high temperature and kept at above 1000 ℃, and the high-temperature gas at the furnace top is used for preheating air through a heat exchanger and supplying air to the lower tuyere and the furnace top tuyere.
10. The blast furnace smelting Cu-Zn separation method according to claim 1, wherein the Cu-Zn material is pretreated when the content of As, Pb, Sb and Bi impurities exceeds a standard, the copper-zinc material particles can be impregnated by sodium hydroxide solution by adopting an impregnation method, the concentration of the sodium hydroxide solution is 80-160 g/L, the mass ratio of the sodium hydroxide solution to the solid material is 3-7: 1, the leaching time is 0.5-2 hours, the leaching temperature is 80-95 ℃, or a sulfuration reduction roasting volatilization dearsenification method can be adopted, 36-58% of copper-zinc material, 36-58% of low-sulfur vulcanizing agent copper blue ore and 2-10% of carbonaceous material are crushed and uniformly mixed, and are made into particles with the diameter of 3-6mm after being humidified by water, then carrying out the sulfuration reduction roasting for 1.5-2.5 hours in a rotary kiln at the temperature of 700-900 ℃.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102345011A (en) * | 2011-10-08 | 2012-02-08 | 昆明理工大学 | Method for producing lead agglomerate by carrying out microwave heating on lead carbonate ore |
| WO2017031574A1 (en) * | 2015-08-24 | 2017-03-02 | 5N Plus Inc. | Processes for preparing various metals and derivatives thereof from copper- and sulfur-containing material |
| CN107686887A (en) * | 2017-08-08 | 2018-02-13 | 赤峰中色锌业有限公司 | Zinc Selenium Removal Process in Hydrometallurgy |
| US10661346B2 (en) | 2016-08-24 | 2020-05-26 | 5N Plus Inc. | Low melting point metal or alloy powders atomization manufacturing processes |
| CN112798364A (en) * | 2020-12-31 | 2021-05-14 | 耒阳市焱鑫有色金属有限公司 | Accurate detection of furnace top CO and CO2Method for increasing blast furnace capacity by ratio |
| CN113355531A (en) * | 2021-05-28 | 2021-09-07 | 河南豫光金铅股份有限公司 | Production method for directly smelting brass raw material into copper anode plate |
| US11607732B2 (en) | 2018-02-15 | 2023-03-21 | 5N Plus Inc. | High melting point metal or alloy powders atomization manufacturing processes |
| CN119194080A (en) * | 2024-10-15 | 2024-12-27 | 河北戴诺思贵金属有限公司 | A method for treating waste catalyst containing copper and zinc |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102345011A (en) * | 2011-10-08 | 2012-02-08 | 昆明理工大学 | Method for producing lead agglomerate by carrying out microwave heating on lead carbonate ore |
| WO2017031574A1 (en) * | 2015-08-24 | 2017-03-02 | 5N Plus Inc. | Processes for preparing various metals and derivatives thereof from copper- and sulfur-containing material |
| CN108138260A (en) * | 2015-08-24 | 2018-06-08 | 伍恩加有限公司 | By the method for the various metals of the material preparation of cupric and sulfur-bearing and its derivative |
| KR20180082425A (en) * | 2015-08-24 | 2018-07-18 | 5엔 플러스 아이엔씨. | Manufacturing process of various metals and their derivatives derived from copper and sulfur |
| US10337083B2 (en) * | 2015-08-24 | 2019-07-02 | 5N Plus Inc. | Processes for preparing various metals and derivatives thereof from copper- and sulfur-containing material |
| KR102113558B1 (en) | 2015-08-24 | 2020-05-21 | 5엔 플러스 아이엔씨. | Manufacturing process of various metals and derivatives derived from copper and sulfur |
| US10661346B2 (en) | 2016-08-24 | 2020-05-26 | 5N Plus Inc. | Low melting point metal or alloy powders atomization manufacturing processes |
| CN107686887A (en) * | 2017-08-08 | 2018-02-13 | 赤峰中色锌业有限公司 | Zinc Selenium Removal Process in Hydrometallurgy |
| US11607732B2 (en) | 2018-02-15 | 2023-03-21 | 5N Plus Inc. | High melting point metal or alloy powders atomization manufacturing processes |
| CN112798364A (en) * | 2020-12-31 | 2021-05-14 | 耒阳市焱鑫有色金属有限公司 | Accurate detection of furnace top CO and CO2Method for increasing blast furnace capacity by ratio |
| CN113355531A (en) * | 2021-05-28 | 2021-09-07 | 河南豫光金铅股份有限公司 | Production method for directly smelting brass raw material into copper anode plate |
| CN119194080A (en) * | 2024-10-15 | 2024-12-27 | 河北戴诺思贵金属有限公司 | A method for treating waste catalyst containing copper and zinc |
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