CN1382814A - Smelting method for separating Cu, Zn and Co from each other - Google Patents
Smelting method for separating Cu, Zn and Co from each other Download PDFInfo
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- CN1382814A CN1382814A CN 02110836 CN02110836A CN1382814A CN 1382814 A CN1382814 A CN 1382814A CN 02110836 CN02110836 CN 02110836 CN 02110836 A CN02110836 A CN 02110836A CN 1382814 A CN1382814 A CN 1382814A
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- 238000000034 method Methods 0.000 title claims abstract description 57
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 53
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 46
- 238000003723 Smelting Methods 0.000 title claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 93
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 74
- 239000010941 cobalt Substances 0.000 claims abstract description 74
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000010949 copper Substances 0.000 claims abstract description 61
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 60
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000002893 slag Substances 0.000 claims abstract description 57
- 239000011701 zinc Substances 0.000 claims abstract description 55
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000011787 zinc oxide Substances 0.000 claims abstract description 29
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 14
- 239000011593 sulfur Substances 0.000 claims abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 7
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- DBQFKMXHMSMNRU-UHFFFAOYSA-N [Zn].[Co].[Cu] Chemical compound [Zn].[Co].[Cu] DBQFKMXHMSMNRU-UHFFFAOYSA-N 0.000 claims description 42
- 235000019738 Limestone Nutrition 0.000 claims description 23
- 239000006028 limestone Substances 0.000 claims description 23
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- 238000002386 leaching Methods 0.000 claims description 17
- 239000003638 chemical reducing agent Substances 0.000 claims description 15
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- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical group C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims description 4
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- 235000013619 trace mineral Nutrition 0.000 description 4
- RMBBSOLAGVEUSI-UHFFFAOYSA-H Calcium arsenate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-][As]([O-])([O-])=O.[O-][As]([O-])([O-])=O RMBBSOLAGVEUSI-UHFFFAOYSA-H 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
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- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- NHPHQYDQKATMFU-UHFFFAOYSA-N [Cu]=S.[Co] Chemical compound [Cu]=S.[Co] NHPHQYDQKATMFU-UHFFFAOYSA-N 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229940030341 copper arsenate Drugs 0.000 description 2
- RKYSWCFUYJGIQA-UHFFFAOYSA-H copper(ii) arsenate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-][As]([O-])([O-])=O.[O-][As]([O-])([O-])=O RKYSWCFUYJGIQA-UHFFFAOYSA-H 0.000 description 2
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- HJTAZXHBEBIQQX-UHFFFAOYSA-N 1,5-bis(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1CCl HJTAZXHBEBIQQX-UHFFFAOYSA-N 0.000 description 1
- MHUWZNTUIIFHAS-XPWSMXQVSA-N 9-octadecenoic acid 1-[(phosphonoxy)methyl]-1,2-ethanediyl ester Chemical compound CCCCCCCC\C=C\CCCCCCCC(=O)OCC(COP(O)(O)=O)OC(=O)CCCCCCC\C=C\CCCCCCCC MHUWZNTUIIFHAS-XPWSMXQVSA-N 0.000 description 1
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 241000784732 Lycaena phlaeas Species 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910007564 Zn—Co Inorganic materials 0.000 description 1
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- Manufacture And Refinement Of Metals (AREA)
Abstract
A smelting method for separating Cu, Zn and Co from the ore material containing Cu (10-50%), Zn (10-40%) and Co (0.2-2%) features that after the said ore material is pretreated from removing harmful impurities or sintered for removing sulfur, it is molten in blass furnace by selective reduction. As a result, the copper in coarse copper mode is discharged, the zinc in zinc oxide is collected from chimny, and the cobalt in slag mode is recovered. Its advantages are high separation effect and metal recovery rate.
Description
Technical Field
The invention relates to the technical field of non-ferrous metallurgy, in particular to the technical field of metallurgy of refractory multi-metal complex ores.
Background
The traditional method for recovering cobalt in copper-cobalt sulfide ore is incidentally recovered in the copper smelting process. The cobalt distribution in the two copper smelting processes, namely the matte smelting process and the converter blowing process is different, about 60-70% of cobalt enters matte during matte smelting, and the rest 30-40% of cobalt enters smelting slag. The white alloy is usually produced by smelting the converter slag which is rich in cobalt, and the cobalt-rich alloy is further processed by a plurality of procedures to obtain a cobalt product. Because the cobalt is distributed and dispersed in the copper smelting process, part of the cobalt is lost in smelting slag, and part of the cobalt is not recovered any more due to low grade of the cobalt. Meanwhile, a large amount of quartz is required to be added for smelting in the blowing process of the copper matteThe cobalt of the agent is low in enrichment multiple in the converter slag, the cobalt-rich slag is low in cobalt grade, the copper grade is high, and the cobalt in the white alloy is enabled to be high
The value is high. That is, the conventional method has a low recovery rate of cobalt because
High value and expensive treatment cost.
The hydrometallurgical process of copper cobalt sulphide ore which was invented and produced later could solve the problem of low cobalt recovery, but the solution was mostly copper, which still required a lot of processing costs in terms of separation and recovery. For copper-zinc-cobalt materials, the technology for effectively separating copper and zinc in a solution is not yet closed, and the copper-zinc-cobalt materials are still in the experimental research stage and cannot be applied to production.
The traditional matte smelting method for copper-zinc-cobalt materials is known to be incapable of normal smelting due to high zinc content.
Disclosure of Invention
The invention aims to solve the technical problem of providing a smelting method for separating copper, zinc and cobalt, which can effectively achieve the purpose of separating copper, zinc and cobalt by one-time smelting, obtains three products that do not contain cobalt in copper basically, zinc oxide does not contain copper and cobalt, cobalt-rich slag contains little copper, is easy to further process to obtain copper, zinc and cobalt metal, and has the characteristics of simple process flow, thorough separation, good comprehensive recovery of various valuable metal components in materials, high metal recovery rate, low recovery cost and good economic benefit.
The technical scheme adopted by the invention for solving the technical problems is as follows: the smelting method for separating copper, zinc and cobalt is characterized in that copper, zinc and cobalt materials with the mass percentages of Cu 10-50%, Zn 10-40% and Co0.2-2.0% are sintered into a sintered block, and then the sintered block, limestone and a carbon-containing reducing agent are mixed according to the following mass ratio by taking the sintered block as a mass reference: 100% of sintered blocks, 15-22% of limestone and 18-25% of carbonaceous reducing agent, the furnace materials are loaded into the top of a blast furnace in batches and in layers, hot air is blown into a blast port at the lower part of the blast furnace for smelting, secondary hot air is blown into a secondary air port at the top of the blast furnace, carbon monoxide and zinc steam in combustion part of furnace gas keep a high-temperature furnace top above 1000 ℃ through heat release of the carbon monoxide and the zinc steam, so as to ensure that zinc oxide is smoothly discharged, a furnace hearth at the bottom of the blast furnace is provided with three layers of melts, namely blister copper, matte and furnace slag, wherein the blister copper and the furnace slag continuously flow into a front bed for separation and discharge, the matte is returned for sintering, the cobalt-rich slag is cast into blocks for.
The carbonaceous reducing agent can be anthracite or petroleum coke besides metallurgical coke.
The sulfur content S of the sintered blocks is less than 1.5%, and the diameter of the blocks is 30-120 mm; the limestone contains more than 50% of CaO containing calcium oxide, and the block diameter is 30-80 mm; the carbon content C of the carbon-containing reducing agent is more than 80 percent, and the block diameter is 30-80 mm.
The blast furnace is a copper-zinc blast furnace, which is different from a common copper smelting blast furnace, has low material columns, and loads some furnace materials into the top of the blast furnace in batches and layers at intervals of a specified time, because the copper-zinc blast furnace is continuously produced, the furnace keeps a certain material column height, a new material batch is loaded along with the descending of the material columns to keep the specified low material column height, the height keeps 1.8-2.2 meters, the temperature of the top of the high-temperature furnace is above 1000 ℃, the main reason of the high-temperature furnace top is that zinc steam is easy to reoxidize into zinc oxide at low temperature, accretion is easy to form in the top and the upper part of the furnace, and the basic furnace operation is influenced, therefore, secondary hot air is blown into the upper part of a material layer of the furnace top, the heat release quantity of the zinc oxide steam and part of carbon monoxide in a material layer of furnace gas is extremely large and reaches above 1000 ℃ quickly, so as to keep. The top structure of the blast furnace is closed, different from that of a common blast furnace, double-bell charging is carried out, high-temperature flue gas is introduced into a vaporization cooling flue and an air heat exchanger, the self-used air of the blast furnace is preheated to a certain temperature such as 300 ℃, and zinc oxide-containing flue gas is cooled by a surface cooler and then is recycled by a bag type dust collector. The section of the tuyere of the blast furnace is small and rectangular, a single-row tuyere is arranged on the cooling water jacket, and hot air is blown into the cooling water jacket for smelting. The hot air is mainly used for strengthening the reduction reaction process of the zinc oxide and saving the consumption of metallurgical coke.
The technical key problem of the invention is to keep the tuyere area of the blast furnace highSo that zinc oxide is easily reduced. The high temperature in the tuyere zone is achieved to ensure the high melting point of the slag. Thus, the blast furnace mixes limestone as a flux to make the slag basicity
The melting point of the slag is above 1050 ℃. The alkalinity of the blast furnace slag varies with the components of the materials to be treated. If the zinc content in the material is low, the alkalinity is reduced, and if the zinc content is high, the opposite is true; if the cobalt content in the material is low and the cobalt-rich slag can not be directly produced, high alkalinity is adopted to ensure that most of cobalt enters the blister copper and is recovered in the blister copper pyrogenic refining slag, and the cobalt-containing grade of the cobalt-rich slag can also reach the same level as that of the former.
Another technical key problem of the invention is to control the reducing atmosphere of the blast furnace, the furnace gas composition before the secondary air blowing in from the top of the blast furnace
The coke rate and the blast volume are adjusted. The control of the reducing atmosphere of the blast furnace also varies with the nature of the material being treated, and if the higher the zinc content in the charge material, the stronger the reducing atmosphere,
the larger the value, the smaller the zinc content the opposite.
If the material treated by the method contains impurities such as arsenic, lead, antimony, bismuth, tin and the like, because the oxides of the impurities are easier to reduce into metal forms than zinc oxide and simultaneously form alloy phases with copper, the further refining of the blister copper is difficult. Therefore, the impurity content of the material which can be treated by the invention is required to be as follows: 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-zinc-cobalt materials which exceed the standard need to be pretreated, and impurities of the copper-zinc-cobalt materials are removed before the copper-zinc-cobalt materials can be smelted by the method.
The pretreatment method is a pyrogenic process, wherein a copper-zinc-cobalt material, a low-sulfur vulcanizing agent chalcocite and a carbonaceous material are mixed according to the mass percentage of 36-58%, 36-58% and 2-10%, are crushed, are mixed uniformly for granulation, and are subjected to vulcanization reduction roasting at the temperature of 700 ℃ and 900 ℃ to obtain roasted sand, namely the pretreated copper-zinc-cobalt material, wherein the main content of each element is
Cu 10～50％； Zn 10～40％；
Co 0.2～2.0％； As ＜0.5％；
Pb ＜0.5％； Sb ＜0.5％；
Sn ＜0.5％； Bi ＜0.4％。
The optimized proportion of the copper-zinc-cobalt material, the low-sulfur vulcanizing agent chalcocite and the carbonaceous material is 46-48%, 46-48% and 4-8%; the diameter of the granulation particles is 3-6 mm; the granulation is carried out after humidifying by water.
The pretreatment method is a wet method, wherein the copper-zinc-cobalt material particles are soaked by a sodium hydroxide solution, the concentration of the sodium hydroxide solution is 110-130 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 ℃, and the leaching residue is the pretreated copper-zinc-cobalt material.
For copper-zinc-cobalt materials with 10-50% of copper, 10-40% of zinc, 0.2-2.0% of cobalt and the rest of gangue, the technical and economic indexes of the new smelting method for separating copper, zinc and cobalt are as follows:
the proportion of furnace charge:
100 percent of sintered cake
15 to 20 percent of limestone
18 to 24 percent of metallurgical coke
Blast furnace hearth energy rate: 40 to 50 tons/m2Day of the day
The product comprises the following components:
90-96% of blister copper Cu; zn 5-6%
85-94% of zinc oxide ZnO; CdO 3-6%
Cobalt-rich slag Co 5-10%; 0.6 percent of Cu0.6 percent and 5 percent of Zn3
The rest of the gangue
Consumption of main auxiliary materials: for 1 ton of crude copper, the amount of metal is
0.5 to 0.9 ton of metallurgical coke
0.2-0.8 ton of limestone
And (3) metal recovery rate:
the recovery rate of copper is 92-97%
The recovery rate of zinc is 85-94%
The recovery rate of cadmium is 92%
The recovery rate of cobalt is 90-92%
Compared with the traditional method, the method has the advantages of simple process flow, thorough copper-zinc-cobalt separation, good comprehensive utilization of multiple metal components, high metal recovery rate, low recovery cost and good economic benefit, and opens up an approach for effectively treating complex multiple metal copper-zinc-cobalt materials.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
The copper-zinc-cobalt material is a high-cobalt material and comprises the following chemical components: cu 30%, Zn 30%, Co1.5%, and the rest gangue components and trace elements. The new smelting method adopts a method for directly obtaining the cobalt-rich slag for the materials. As the valuable components of Cu, Zn and Co in the material are extremely high, the total content is up to 61.5 percent, the oxygen content of the oxide shape is up to 90 percent, and the gangue component, namely the slagging part is very little. The smelting method adopts a partial self-produced blast furnace slag returning smelting method to directly produce the cobalt-rich slag.
100% of sintered blocks, 15% of limestone and 18% of metallurgical coke are loaded into the top of a blast furnace in batches and in layers by taking the sintered blocks as a reference, hot air is blown into a blast port at the lower part of the blast furnace for smelting, secondary hot air is blown into a secondary air port at the top of the blast furnace, carbon monoxide and zinc steam in part of furnace gas are combusted, the temperature of the furnace top is kept to be higher than 1000 ℃ by heat release of the carbon monoxide and the zinc steam, so as to ensure that zinc oxide is smoothly discharged, a hearth at the bottom of the blast furnace is provided with three layers of melts, namely blister copper, matte and furnace slag, wherein the blister copper and the furnace slag continuously flow into a front bed for separation and discharge, the matte is returned for sintering, the cobalt-rich.
The method comprises the following steps of sintering materials, wherein one purpose is that sulfur in a sintered block is lower than 1.5%, the second purpose is that a powdery material is agglomerated into blocks, the particle diameter is in a range of 30-120mm, and the blast furnace smelting is facilitated, and similarly, limestone contains more than 50% of calcium oxide CaO, the block diameter is 30-80 mm, the carbon content C of metallurgical coke containing a carbon-containing reducing agent is more than 80%, the block diameter is 30-80 mm, and the mechanical strength and the activity are required to be high and low.
In order to maintain a high temperature in the tuyere region of the blast furnace so that zinc oxide is easily reduced. The high temperature in the tuyere zone is achieved to ensure the high melting point of the slag. Thus, the blast furnace mixes limestone as a flux to make the slag alkalineDegree of rotationThe melting point of the slag is above 1050 ℃.
Adding metallurgical coke containing carbon reducer and regulating air-material ratio to make the furnace fume be before secondary air is blown
1, maintaining a normal reducing atmosphere.
And continuously filling a new batch of materials to keep the specified low column height along with the descending of the column, wherein the height of the column is kept to be 1.8-2.2 m. Secondary hot air, zinc oxide steam and part of carbon monoxide in furnace gas are blown into the upper part of the furnace top material layer, the heat release quantity is extremely large and reaches more than 1000 ℃ quickly, so that the normal descending of furnace burden and the discharge of zinc oxide are maintained. The top structure of the blast furnace is closed, different from that of a common blast furnace, double-bell charging is carried out, high-temperature flue gas is introduced into a vaporization cooling flue and an air heat exchanger, the self-used air of the blast furnace is preheated to a certain temperature such as 300 ℃, and zinc oxide-containing flue gas is cooled by a surface cooler and then is recycled by a bag type dust collector. The section of the tuyere of the blast furnace is small and rectangular, a single-row tuyere is arranged on the cooling water jacket, and hot air is blown into the cooling water jacket for smelting.
The following chemical reactions take place at high temperatures in the tuyere zone of the blast furnace:
CuO in the sintered cake is most easily reduced into metallic copper, and ZnO is reduced into metallic zinc, and the metallic zinc rises along with flue gas in a steam state at high temperature. Part of cobalt oxide and iron oxide is inevitably reduced into metal cobalt and metal iron in the smelting process, but when zinc oxide exists, the cobalt oxide and the iron oxide are quickly replaced by the zinc oxide and are oxidized again into the slag. Thus, copper is reduced into blister copper, zinc is reduced into zinc steam, the zinc steam rises to the top of the furnace and is oxidized into zinc oxide when meeting secondary air, and cobalt enters blast furnace slag and is produced in the form of cobalt-rich slag.
Since the agglomerates contain a small amount of sulphur, a small amount of matte is produced, the amount of which does not exceed 2% by weight of the agglomerates. Thus, three products are in the hearth, and three layers are formed due to different specific gravities of the products. The bottom is blister copper, which is discharged intermittently in a siphon manner and cast into ingots. The matte and the slag continuously flow into the front bed from the other port for further separation, the slag is continuously discharged and cast into blocks, and the matte is discharged discontinuously and returns to sintering.
If the copper-zinc-cobalt material in each batch contains arsenic, lead, antimony, bismuth, tin and other impurities exceeding the standard, pretreatment is carried out, wherein a sulfuration reduction roasting method can be adopted, 47% of copper-zinc-cobalt material, 47% of low-sulfur vulcanizing agent chalcocite and 6% of carbonaceous material coke powder are mixed according to the mass percentage, and the preferable mass ratio of copper to sulfur of the low-sulfur vulcanizing agent chalcocite is more than 2. Then, the material is ball-milled and crushed by a ball mill, and the particles are as fine as possible in principle, and the ball milling is generally performed at about 100 meshes. And then selecting a binding agent, wherein water is preferably used, humidifying and granulating, the particle size can be adapted to a roasting furnace in principle, and no special requirement is needed, but the particle diameter is controlled within the range of 3-6mm in order to take reaction effect and granulation cost into consideration. At 800 deg.c, sulfurizing, reducing and roasting in a rotary kiln with non-oxidizing atmosphere for 1.5-2.5 hr, preferably 2 hr. The roasted calcine is used as the copper-zinc-cobalt material for new smelting method.
The chemical process mainly comprises the following steps:
the arsenic in the Cu-Zn-Co material exists mostly in the form of copper arsenate, which is chemically decomposed during roasting
Reduction of copper oxide to copper by carbon or carbon monoxide in the presence of a reducing agent such as coke powder
Meanwhile, the chalcocite decomposes sulfur vapor under the reducing atmosphere and combines with copper to generate stable Cu2S, the combination of the subsequently generated arsenic and the metallic copper is prevented, and the arsenic is volatilized and removed in the form of arsenic trioxide or arsenic vapor.
The method consumes reducing agent coke powder, the added vulcanizing agent chalcocite is a copper raw material of the company, the main consumption is heavy oil consumption of the rotary kiln, and therefore the pretreatment smelting cost is low.
The pretreatment can also adopt a wet method, sodium hydroxide solution is soaked in copper-zinc-cobalt material particles, the concentration of the sodium hydroxide solution is 120 g/L, the mass ratio of the sodium hydroxide solution to solid materials is 5: 1, the leaching time is 1 hour, the leaching temperature is 90 ℃, three-section countercurrent soaking is adopted, and the obtained leaching residue is the pretreated copper-zinc-cobalt material. Meanwhile, arsenic, lead, zinc and mirabilite are recovered from the impregnation liquid. The method comprises the steps of dipping copper-zinc-cobalt material particles into a sodium hydroxide solution to obtain a leaching solution, concentrating and crystallizing, recycling mother liquor to dip the copper-zinc-cobalt material, dissolving a crystallization mixture in water, and replacing the crystallization mixture with calcium hydroxide, wherein the amount of lime with low price is more than three times of that of theoretical calculation amount, sodium arsenate generates precipitated calcium arsenate and regenerated alkali sodium hydroxide, and a part of mirabilite is also converted into regenerated alkali sodium hydroxide, so that a large amount of regenerated alkali is increased, the mother liquor is concentrated and crystallized to generate mirabilite after the calcium arsenate is recovered, and then washing leaching residues with residual liquor and recycling the leached copper-zinc-cobalt material. As the calcium arsenate is used as the pesticide product, the solution can be completely recycled, no sewage is discharged, and the environmental protection of air and water sources is achieved.
The main chemical reaction process is as follows:
when the sodium hydroxide solution is used for soaking the copper-zinc-cobalt material particles, arsenic in the material mainly exists in the form of copper arsenate and chemically reacts with sodium hydroxide. The following chemical reactions occur when lime is added to the impregnation liquor. Thereby generating a large amount of regenerated alkali, recycling residual liquid and simultaneously recoveringCalcium arsenate is used as pesticide. For 1 ton of material pretreatment, main medicament consumption: NaOH 150 kg Ca (OH)2The cost is low because of 80 kg of coal and 500 kg of coal, the process is scientific and reasonable, and the implementation is easy. The technical and economic indexes of the new smelting method for separating copper, zinc and cobalt are as follows: the furnace burden proportion is as follows:
100 percent of sintered cake
15 percent of limestone
Metallurgical coke 18% blast furnace hearth energy rate: 50 ton/m2Dailyproduct ingredients:
blister copper Cu 94%, Zn 4%
ZnO 90% and CdO 6%
Co 8% of cobalt-rich slag, Cu 0.6%, Zn 3-5%,
Metallurgical coke 0.5 ton
0.4 ton metal recovery rate of limestone:
the recovery rate of copper is 97 percent
The recovery rate of zinc is 90 percent
The recovery rate of cadmium is 92%
The recovery rate of cobalt is 94 percent
Example 2
The copper-zinc-cobalt material used in the embodiment is a low-cobalt material, and the chemical components of the material are as follows: cu 25%, Zn 25%, Co0.5%, and the rest of gangue and trace elements. The invention adopts a method for indirectly obtaining the cobalt-rich slag for treating the materials. Because the materials contain more slagging elements and less cobalt, the cobalt-rich slag cannot be directly produced. Therefore, the blast furnace adopts higher alkalinity and reducing atmosphere for smelting, so that most of cobalt enters the blister copper, and the cobalt in the blister copper is recovered in the anode refining oxidation slag, thereby obtaining the cobalt-rich slag with the same grade as that of the example 1.
In order to maintain a high temperature in the tuyere region of the blast furnace so that zinc oxide is easily reduced. The high temperature in the tuyere zone is achieved to ensure the high melting point of the slag. The blast furnace mixes limestone as flux to make slag alkalinity
The melting point of the slag is above 1050 ℃.
Adding metallurgical coke containing carbon reducer and regulating air-material ratio to make the furnace fume be before secondary air is blownA normal reducing atmosphere is maintained.
The technical and economic indexes of the new smelting method for separating copper, zinc and cobalt are as follows:
the furnace burden proportion is as follows:
100 percent of sintered cake
20 percent of limestone
Anthracite 20 percent
Blast furnace hearth energy rate: 50 ton/m2Day of the day
The product comprises the following components:
blister copper Cu 90%, Zn 1%, Co2.5%
ZnO 90% and CdO 6%
Co 12% of cobalt-rich slag, Cu 2%,
consumption of main auxiliary materials: for 1 ton of blister copper, the amount of metal is
Anthracite coal 0.9 ton
0.9 ton metal recovery of limestone:
the recovery rate of copper is 95 percent
The recovery rate of zinc is 90 percent
The recovery rate of cobalt is 88 percent
The pretreatment of the copper-zinc-cobalt material can adopt a pyrogenic process, the mass percentages of the copper-zinc-cobalt material, the low-sulfur vulcanizing agent chalcocite and the carbonaceous material coal dust are 58%, 36%, and the roasting temperature is controlled at 700 ℃, and the rest is as in example 1.
The copper-zinc-cobalt material pretreatment can also adopt a wet method, the concentration of the sodium hydroxide solution is 110 g/L, the mass ratio of the sodium hydroxide solution to the solid material is 7: 1, the leaching time is 2 hours, the leaching temperature is 80 ℃, four-section countercurrent impregnation is adopted, and the others are as in example 1.
Example 3
The material treated in this example is a copper-zinc-cobalt material with low zinc content, and its chemical composition is Cu 30%, Zn 10%, Co1.0%, and the rest gangue components and trace elements. Because the material contains more slagging elements, although the cobalt content is high, the satisfactory cobalt-rich slag can not be produced. Therefore, cobalt-rich slag was obtained under the same technical conditions as in example 2.
In order to maintain a high temperature in the tuyere region of the blast furnace so that zinc oxide is easily reduced. The high temperature in the tuyere zone is achieved to ensure the high melting point of the slag. The blast furnace mixes limestone as flux to make slag alkalinityThe melting point of the slag is above 1050 ℃.
Adding metallurgical coke containing carbon reducer and regulating air-material ratio to make the furnace fume be before secondary air is blown
A normal reducing atmosphere is maintained.
The technical and economic indexes are as follows:
the furnace burden proportion is as follows:
100 percent of sintered cake
20 percent of limestone
20 percent of metallurgical coke
Blast furnace hearth energy rate: 50 ton/m2Day of the day
The product comprises the following components:
blister copper Cu 90%, Zn 1%, Co3.4%
ZnO 88%
Co 18% of cobalt-rich slag, Cu 2%,
consumption of main auxiliary materials: according to the production of 1 ton of crude copper, the metal amount
Metallurgical coke 0.7 ton
Limestone 0.7 ton
And (3) metal recovery rate:
the recovery rate of copper is 97 percent
The recovery rate of zinc is 85 percent
The recovery rate of cobalt is 92 percent
The pretreatment of the copper-zinc-cobalt material can adopt a pyrogenic process, the mass percentages of the copper-zinc-cobalt material, the low-sulfur vulcanizing agent chalcocite 58 and the carbonaceous material coke powder 6 are controlled, and the roasting temperature is controlled at 900 ℃, otherwise, the pretreatment is as in example 1.
The copper-zinc-cobalt material pretreatment can also adopt a wet method, the concentration of the sodium hydroxide solution is 130 g/L, the mass ratio of the sodium hydroxide solution to the solid material is 3: 1, the leaching time is 0.5 hour, the leaching temperature is 95 ℃, three-section countercurrent impregnation is adopted, and the others are as in example 1.
Example 4
The material treated by the embodiment is a material with high copper, high zincand low cobalt, and the chemical components of the material are as follows: cu 25%, Zn 40%, Co0.8%, and the balance of gangue and trace elements. Although the cobalt content of the material is low, the slag-making element content in the material is low, and the slag yield is low, so that the cobalt-rich slag can be directly obtained. However, blast furnace smelting of high zinc materials requires a certain amount of slag to keep the blast furnace moving forward. In order to not reduce the cobalt grade of the cobalt-rich slag, the blast furnace operation adopts a partial slag return smelting method to ensure that the cobalt-rich slag is produced, and the technical and economic indexes are as follows:
the furnace burden proportion is as follows:
100 percent of sintered cake
Limestone 22%
Petroleum coke 25%
Blast furnace hearth energy rate: 45 ton/m2Day of the day
The product comprises the following components:
crude copper Cu 93%, Zn 5%
Zinc oxide ZnO 92%
Co 10% of cobalt-rich slag, Cu 0.6%,
consumption of main auxiliary materials: for 1 ton of crude copper, the amount of metal is
Petroleum coke 0.9 ton
Limestone 0.8 ton
And (3) metal recovery rate:
the recovery rate of copper is 96 percent
The recovery rate of zinc is 92%
The recovery rate of cobalt is 90 percent
The pretreatment of the copper-zinc-cobalt material can adopt a pyrogenic process, the masspercentages of the copper-zinc-cobalt material, the low-sulfur vulcanizing agent chalcocite and the carbonaceous material coke powder are 47 percent, and the roasting temperature is controlled at 800 ℃, otherwise, the pretreatment is as in example 1.
The copper-zinc-cobalt material pretreatment can also adopt a wet method, the concentration of the sodium hydroxide solution is 120 g/L, the mass ratio of the sodium hydroxide solution to the solid material is 5: 1, the leaching time is 1 hour, the leaching temperature is 90 ℃, three-section countercurrent impregnation is adopted, and the others are as in example 1.
Claims (10)
1. A smelting method for separating copper, zinc and cobalt is characterized in that copper, zinc and cobalt materials with the mass percentages of Cu 10-50%, Zn 10-40% and Co0.2-2.0% are sintered into a sintered block, and then the sintered block, limestone and a carbon-containing reducing agent are mixed according to the following mass ratio by taking the sintered block as a mass standard:
100 percent of sintered cake
15 to 22 percent of limestone
18-25% of carbonaceous reducing agent is loaded into the top of a blast furnace in batches and in layers, hot air is blown into a blast port at the lower part of the blast furnace for smelting, secondary hot air is blown into a secondary air port arranged on the top of the blast furnace, carbon monoxide and zinc steam in partial furnace gas are combusted, the temperature of the furnace top is kept to be higher than 1000 ℃ by heat release of the carbon monoxide and the zinc steam, so that zinc oxide is smoothly discharged, three layers of melts are arranged in a hearth at the bottom of the blast furnace, namely blister copper, matte and furnace slag, the matte and the furnaceslag continuously flow into a front bed to be separated and discharged, the matte is returned to be sintered, cobalt-rich slag is cast into blocks to further recover cobalt, and the blister.
2. The method of claim 1, wherein the carbonaceous reductant is anthracite or petroleum coke, in addition to metallurgical coke.
3. The method according to claim 1, characterized in that the sintered cake has a sulfur content S<1.5%, a cake diameter of 30-120 mm; the limestone contains more than 50% of CaO containing calcium oxide, and the block diameter is 30-80 mm; the carbon content C of the carbon-containing reducing agent is more than 80 percent, and the block diameter is 30-80 mm.
4. The method according to claim 1, wherein 15-22% limestone is added to make the slag basicityEnsuring the melting point of the slag to be above 1050 ℃.
5. The method according to claim 1, wherein 18-25% of carbonaceous reducing agent is added, and the air-fuel ratio is adjusted to ensure that the furnace flue gas is blown with secondary air before
A normal reducing atmosphere is maintained.
6. The method according to claim 1, wherein said blast furnace is a copper-zinc blast furnace, which is different from a general copper-smelting blast furnace in that the burden column is low and kept at a height of 1.8-2.2 m, the top temperature of the furnace is above 1000 ℃, the tuyere ratio is small, and the sealing performance of the top gas is good.
7. The method of claim 6, characterized in that the high-temperature flue gas discharged from the furnace top is preheated by a heat exchanger, the preheated air is used for the lower tuyere and the secondary tuyere on the furnace top, and the zinc oxide product is recovered by a bag type dust collector after the flue gas is cooled by a surface cooler.
8. The method as claimed in claim 1, wherein the copper-zinc-cobalt material is pretreated by mixing the copper-zinc-cobalt material, the low-sulfur vulcanizing agent chalcocite and the carbonaceous material in the mass percentages of 36-58%, 36-58% and 2-10%, pulverizing, mixing, uniformly granulating, and then performing vulcanization reduction roasting at the temperature of 700 ℃ and 900 ℃ to obtain the roasted product, i.e. the pretreated copper-zinc-cobalt material, wherein the main contents of the elements are
Cu 10～50％； Zn 10～40％；
Co 0.2～2.0％； As ＜0.5％；
Pb ＜0.5％ ； Sb ＜0.5％；
Sn ＜0.5％； Bi ＜0.4％。
9. The method of claim 8, wherein the copper zinc cobalt material, the low-sulfur vulcanizing agent chalcocite and the carbonaceous material are preferably mixed in a ratio of 46-48%, 46-48% and 4-8%; the diameter of the granulation particles is 3-6 mm; the granulation is carried out after humidifying by water.
10. The method as claimed in claim 1, wherein the copper-zinc-cobalt material is pretreated by impregnating particles of the copper-zinc-cobalt material with a sodium hydroxide solution, the concentration of the sodium hydroxide solution is 110-130 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 ℃, and the leaching residue is the pretreated copper-zinc-cobalt material.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100371476C (en) * | 2004-01-19 | 2008-02-27 | 住友金属矿山株式会社 | Slag fumigation method |
| RU2398031C1 (en) * | 2009-09-10 | 2010-08-27 | Федеральное государственное образовательное учреждение высшего профессионального образования "Сибирский федеральный университет" | Procedure for depletion of solid copper-zinc slag |
| CN101338373B (en) * | 2008-08-14 | 2011-05-18 | 上饶市华丰铜业有限公司 | Method for producing smelting copper-cobalt oxidation ore by blast furnace |
| CN109609776A (en) * | 2019-02-14 | 2019-04-12 | 平罗县中兴碳素有限公司 | A method for extracting copper and cobalt in copper converter slag by using waste cathode carbon block of aluminum electrolysis cell |
-
2002
- 2002-02-08 CN CNB021108366A patent/CN1188533C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100371476C (en) * | 2004-01-19 | 2008-02-27 | 住友金属矿山株式会社 | Slag fumigation method |
| CN101338373B (en) * | 2008-08-14 | 2011-05-18 | 上饶市华丰铜业有限公司 | Method for producing smelting copper-cobalt oxidation ore by blast furnace |
| RU2398031C1 (en) * | 2009-09-10 | 2010-08-27 | Федеральное государственное образовательное учреждение высшего профессионального образования "Сибирский федеральный университет" | Procedure for depletion of solid copper-zinc slag |
| CN109609776A (en) * | 2019-02-14 | 2019-04-12 | 平罗县中兴碳素有限公司 | A method for extracting copper and cobalt in copper converter slag by using waste cathode carbon block of aluminum electrolysis cell |
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