CN1188533C - 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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- CN1188533C CN1188533C CNB021108366A CN02110836A CN1188533C CN 1188533 C CN1188533 C CN 1188533C CN B021108366 A CNB021108366 A CN B021108366A CN 02110836 A CN02110836 A CN 02110836A CN 1188533 C CN1188533 C CN 1188533C
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- 238000000034 method Methods 0.000 title claims abstract description 57
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 34
- 238000003723 Smelting Methods 0.000 title claims abstract description 28
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 84
- 239000010941 cobalt Substances 0.000 claims abstract description 64
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 63
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000002893 slag Substances 0.000 claims abstract description 59
- DBQFKMXHMSMNRU-UHFFFAOYSA-N [Zn].[Co].[Cu] Chemical compound [Zn].[Co].[Cu] DBQFKMXHMSMNRU-UHFFFAOYSA-N 0.000 claims abstract description 57
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000010949 copper Substances 0.000 claims abstract description 42
- 239000011787 zinc oxide Substances 0.000 claims abstract description 30
- 239000011701 zinc Substances 0.000 claims abstract description 28
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000008569 process Effects 0.000 claims abstract description 24
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- 239000000292 calcium oxide Substances 0.000 claims description 13
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 13
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- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims description 5
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052787 antimony Inorganic materials 0.000 abstract description 2
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- 229910052797 bismuth Inorganic materials 0.000 abstract description 2
- 238000009856 non-ferrous metallurgy Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 abstract 1
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- 235000013495 cobalt Nutrition 0.000 description 60
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- 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 4
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- 239000003818 cinder Substances 0.000 description 3
- 238000009867 copper metallurgy Methods 0.000 description 3
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- 229910001361 White metal Inorganic materials 0.000 description 2
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- PEEDYJQEMCKDDX-UHFFFAOYSA-N antimony bismuth Chemical compound [Sb].[Bi] PEEDYJQEMCKDDX-UHFFFAOYSA-N 0.000 description 2
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- 238000010276 construction Methods 0.000 description 2
- RKYSWCFUYJGIQA-UHFFFAOYSA-H copper(ii) arsenate Chemical group [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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- 239000004571 lime Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 239000010969 white metal Substances 0.000 description 2
- 101100328886 Caenorhabditis elegans col-2 gene Proteins 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 238000007664 blowing Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
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- UPWOEMHINGJHOB-UHFFFAOYSA-N cobalt(III) oxide Inorganic materials O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 1
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention relates to the technical field of non-ferrous metallurgy, particularly to smelting technology of multi-metal complicated ore which is difficult to process; more specifically, the present invention relates to a copper-zinc-cobalt separating smelting method. The copper-zinc-cobalt separating smelting method aims to effectively separate copper-zinc-cobalt material comprising 10% to 50% of copper, 10% to 40% of zinc and 0.2% to 2.0% of cobalt by using a smelting method so as to obtain three easily recycled products. The copper-zinc-cobalt separating smelting method is characterized in that after the copper-zinc-cobalt material is preprocessed to remove harmful impurities, such as arsenic, lead, bismuth, antimony, tin, etc., the copper-zinc-cobalt material is sintered, desulfurized and loaded into a blast furnace so as to be selectively recovered and smelted; in one furnace, the copper is released in a furnace crucible in the form of raw copper, the zinc is collected from top smoke in the form of zinc oxide, and the cobalt is recovered in the form of cobalt-enriched slag. The technologic method has the characteristics of simple process, thorough separation of the copper, the zinc and the cobalt, good comprehensive utilization of various valuable metal components, high metal recovery rate, low smelting processing cost and good economic benefits, and opens up a new path for smelting complicated material which is difficult to process.
Description
Technical field
The present invention relates to a kind of non-ferrous metallurgy technology field, particularly relate to the metallurgical technology field in unmanageable multi-metal complex ore deposit.
Background technology
The traditional method that cobalt reclaims in the copper cobalt sulfide ore is to reclaim in passing in the copper metallurgy process.Two operations of copper metallurgy, i.e. matte smelting and bessemerize in the operation cobalt and distribute differently, about 60～70% cobalts enter matte during matte smelting, and all the other 30～40% enter smelting slag.Usually carry out melting and produce white metal containing the rich converter slag of cobalt, its rich cobalt-base alloy again a step with working procedures handle the cobalt product.Because cobalt distributes and disperses in the copper metallurgy process, the part cobalt is lost in the smelting slag, and its part is low because of the cobalt grade, no longer reclaims.Need add a large amount of quartzy flux during matte blowing simultaneously, its cobalt enrichment multiple in converter slag is low, and rich cobalt slag cobalt grade is low, and the copper grade height makes in the white metal
Value is high.That is to say that it is low that traditional method has the cobalt rate of recovery, because of
Value is high, the problem of its processing costs costliness.
The hydrometallurgical processes of the copper cobalt sulfide ore of inventing afterwards and producing can solve the low problem of the cobalt rate of recovery, but the overwhelming majority is a copper in the solution, and its separation and recovery aspect still need a large amount of tooling costs.Concerning the material of copper zinc cobalt and since solution in effectively separating copper zinc technology also do not reach a standard, still be in the experimental study stage, fail to produce application.
Traditional matte smelting method of copper zinc cobalt material is handled, and is well-known, all can't carry out normal smelting because zinc content is too high.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of copper zinc cobalt isolating smelting process at prior art, its melting once can effectively reach copper zinc cobalt and separate purpose, obtaining three kinds of products is not contain cobalt in the copper basically, not cupric and cobalt in the zinc oxide, and cupric is few in the rich cobalt slag, be easy to further handle obtain copper zinc cobalt metal, and it is simple to have technical process, separate thoroughly, the comprehensive recovery of each valuable metal component well in the material, the metal recovery rate height, cost recovery is low, good in economic efficiency characteristics.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: the isolating smelting process of this kind copper zinc cobalt, it is characterized in that with mass percent be Cu10～50%, Zn10～40%, the copper zinc cobalt material of Co0.2～2.0%, through sintering agglomerate into, then with agglomerate, Wingdale and carbon containing reducer are quality criteria with the agglomerate by following quality proportioning: agglomerate 100%, Wingdale 15～22%, carbon containing reducer 18～25%, these furnace charges blast furnace top of hierarchically packing into, blast furnace bottom blast orifice blasts warm air and carries out melting, furnace roof is provided with overfiren air port and also blasts secondary hot-air, carbon monoxide and zinc fume in the combustion parts furnace gas, keep high temperature furnace roof more than 1000 ℃ by its heat release, to guarantee the smooth and easy discharge of zinc oxide, blast furnace bottom cupola well has three layers of melt, be respectively blister copper, matte and slag, matte and slag continuously flow into external crucible to be separated and emits, and matte returns sintering, and rich cobalt slag is cast the block cobalt that further reclaims, blister copper is regularly emitted ingot casting, sends to refining; Technical key issue of the present invention is to keep blast furnace tuyere zone high temperature, so that zinc oxide is easy to obtain reduction, the high temperature of its tuyere zone reaches to guarantee the slag high-melting-point, and therefore, blast furnace is allocated Wingdale into as flux, makes basicity of slag
Slag melting is more than 1050 ℃, and this blast-furnace cinder basicity should change to some extent with the composition difference of handling material.If it is low to contain zinc in the material, answer basicity to reduce, it is then opposite to contain the zinc height, if it is low to contain the cobalt amount in the material, directly during the rich cobalt slag of output, just adopt high basicity, make most of cobalt advance blister copper, and reclaim in blister copper pyrorefining slag, its rich cobalt slag contains the cobalt grade also can reach with the former par; Another key problem in technology problem of the present invention is the reducing atmosphere of control blast furnace, the composition of fumes before the furnace roof secondary air blasts
To regulate the control of burnt rate and blast volume method, the control of blast furnace reduction atmosphere also should be different to some extent with the character of handling material, to heal by force if contain the zinc high reducing atmosphere of healing in the furnace charge,
It is big that value is wanted, and zinc content is more opposite.
Above-mentioned carbon containing reducer is except that metallurgical coke, can also be with hard coal or refinery coke.
Above-mentioned agglomerate sulphur content S＜1.5%, piece diameter 30～120mm; Wingdale contains calcium oxide CaO＞50%, piece diameter 30～80mm; Carbon containing reducer carbon content C＞80%, piece diameter 30～80mm.
Above-mentioned employing blast furnace is a copper zinc blast furnace, different with general copper blast furnace, stock column is low, these some furnace charges blast furnace top of hierarchically packing at interval in required time in batches, because copper zinc blast furnace is a quantity-produced, keep certain stock column height in the stove, descend with stock column, the new batch of material of packing into keeps the low column height stipulated, it highly keeps 1.8～2.2 meters, high temperature furnace roof, throat temperature are more than 1000 ℃, and the major cause of its high temperature furnace roof is because zinc fume easily is reoxidised into zinc oxide under low temperature, it easily forms furnace accretion in the furnace roof and the top bed of material, influence basic furnace operating, for this reason, furnace roof bed of material top blasts the secondary warm air, part carbon monoxide in zinc oxide steam and the furnace gas, its thermal discharge is very big, reaches very soon more than 1000 ℃, with the normal decline of maintenance furnace charge and the discharge of zinc oxide.Top construction is not both airtight with general blast furnace, the double-charging bell charging, high-temperature flue gas imports gasification cooling flue and air heat exchanger, the personal preheating of air of blast furnace to certain temperature as 300 ℃, contain the zinc oxide flue gas and reclaim zinc oxide product through the surface cooler back bag filter that cools.Blast furnace air port section ratio is less, is rectangle, and watercooling jacket is provided with single air outlet, blasts hot blast and carries out melting.The main purpose of using hot blast is to strengthen the reduction reaction process of zinc oxide and save metallurgical coke consumption.
The handled material of this method if contain impurity such as plumbous antimony bismuth of arsenic and tin, because its oxide compound all than the easy metal form that is reduced into of zinc oxide, all easily forms alloy phase with copper simultaneously, adds to the difficulties for the further refining of blister copper.Therefore the treatable material foreign matter content of the present invention institute requires: As＜0.5%, Pb＜0.5%, Sb＜0.5%, Sn＜0.5%, Bi＜0.4%.
Just pre-treatment must be carried out for the copper zinc cobalt material that exceeds above-mentioned standard, this law melting could be supplied after removing its impurity.
Pretreatment process is that pyrogenic process is according to mass percent 36-58%, 36-58%, 2-10% proportioning with copper zinc cobalt material, low-sulfur vulcanizing agent copper glance, carbonaceous material, mix granulation after the pulverizing, under temperature 700-900 ℃, carry out the reversion roasting then, obtaining calcining is exactly pretreated copper zinc cobalt material, and the main content of its 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％。
Above-mentioned copper zinc cobalt material, low-sulfur vulcanizing agent copper glance, carbonaceous material optimum ratio are 46-48%, 46-48%, 4-8%; The granulation particle dia is in the 3-6mm size; Granulation is carried out granulation after adopting the water humidification.
Pretreatment process is that wet method is to adopt sodium hydroxide solution dipping copper zinc cobalt material particles, concentration of sodium hydroxide solution is at the 110-130 grams per liter, sodium hydroxide solution and solid materials quality proportioning are 3-7: 1, extraction time was at 0.5-2 hour, extraction temperature is at 80-95 ℃, and leached mud is exactly pretreated copper zinc cobalt material.
To copper 10～50%, it is as follows that zinc 10～40%, cobalt 0.2～2.0%, the copper zinc cobalt material of all the other gangues, copper zinc cobalt separate the technico-economical comparison of new smelting process:
The proportioning of furnace charge:
Agglomerate 100%
Wingdale 15～20%
Metallurgical coke 18～24%
Blast furnace specific capacity: 40～50 tons/meter
2Day
Product composition:
Blister copper Cu90～96%; Zn5～6%
Zinc oxide ZnO85～94%; CdO3～6%
Rich cobalt slag Co5～10%; Cu0.6%, Zn3～5%
All the other gangues
Main subsidiary material consumption:, be amount of metal to producing 1 ton of blister copper
0.5～0.9 ton of metallurgical coke
0.2～0.8 ton in Wingdale
Metal recovery rate:
Copper recovery 92～97%
Zinc recovery 85～94%
The cadmium rate of recovery 92%
The cobalt rate of recovery 90～92%
This method is compared with traditional method, and it is simple to have a technical process, and copper zinc cobalt separates thoroughly, the comprehensive utilization of many metal components is made good use of, the metal recovery rate height, and cost recovery is low, good in economic efficiency advantage has been opened up an approach to effective processing of complex multi-metal copper zinc cobalt material.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail.
Embodiment 1
Used copper zinc cobalt material is high cobalt material, and its chemical ingredients is: Cu30%, Zn30%, Col.5%, all the other gangue contents and trace element.To its material, new smelting process adopts the rich cobalt slag method that directly obtains.Because copper zinc cobalt valuable component is high in the material, add up to up to 61.5%, comprise its oxide shape institute oxygen level up to 90%, and gangue content be the slag making part seldom.This melting rule adopts the self-produced blast-furnace cinder Returning smelting of part method, directly the rich cobalt slag of output.
With agglomerate 100%, Wingdale 15%, metallurgical coke 18%, with the agglomerate is benchmark, these furnace charges blast furnace top of hierarchically packing in batches, blast furnace bottom blast orifice blasts warm air and carries out melting, furnace roof is provided with overfiren air port and also blasts secondary hot-air, carbon monoxide and zinc fume in the combustion parts furnace gas, keep high temperature furnace roof more than 1000 ℃ by its heat release, to guarantee the smooth and easy discharge of zinc oxide, blast furnace bottom cupola well has three layers of melt, is respectively blister copper, matte and slag, matte and slag continuously flow into external crucible to be separated and emits, matte returns sintering, and rich cobalt slag is cast the block cobalt that further reclaims, and blister copper is regularly emitted ingot casting.
Material is earlier through oversintering, its purpose has two, and promptly one is that sulfur-bearing reaches that to be lower than 1.5%, the second purpose be that pulverulent material is formed bulk in the agglomerate, reach particle diameter in the 30-120mm scope, help blast furnace smelting, in like manner, Wingdale contains calcium oxide CaO＞50%, piece diameter 30～80mm, carbon containing reducer metallurgical coke carbon content C＞80%, piece diameter 30～80mm requires the physical strength height and activity is low.
For keeping blast furnace tuyere zone high temperature, so that zinc oxide is easy to obtain reduction.The high temperature of its tuyere zone reaches to guarantee the slag high-melting-point.Therefore, blast furnace is allocated Wingdale into as flux, makes basicity of slag
Slag melting is more than 1050 ℃.
Add the carbon containing reducer metallurgical coke, regulate wind material ratio simultaneously and make kiln gas before blasting secondary air
, keep normal reducing atmosphere.
Descend with stock column, the new batch of material of constantly packing into keeps the low column height stipulated, and it highly keeps 1.8～2.2 meters.Furnace roof bed of material top blasts the secondary warm air, part carbon monoxide in zinc oxide steam and the furnace gas, and its thermal discharge is very big, reaches very soon more than 1000 ℃, with the normal decline of maintenance furnace charge and the discharge of zinc oxide.Top construction is not both airtight with general blast furnace, the double-charging bell charging, high-temperature flue gas imports gasification cooling flue and air heat exchanger, the personal preheating of air of blast furnace to certain temperature as 300 ℃, contain the zinc oxide flue gas and reclaim zinc oxide product through the surface cooler back bag filter that cools.Blast furnace air port section ratio is less, is rectangle, and watercooling jacket is provided with single air outlet, blasts hot blast and carries out melting.
Issue at blast furnace tuyere zone high temperature and to give birth to the row chemical reaction:
Secondly the easiest metallic copper that is reduced into of CuO in the agglomerate is ZnO, and ZnO is reduced into metallic zinc, at high temperature becomes steam condition to rise with flue gas.Partial oxidation cobalt and ferric oxide also are reduced into cobalt metal and metallic iron inevitably in fusion process, but very fast oxidized zinc displacement when zinc oxide is arranged, and are oxidized to cobalt oxide again and ferric oxide enters slag.Guarantee that like this copper reduction becomes blister copper, zinc is reduced into zinc fume and rises to furnace roof, meets secondary air and is reoxidised into zinc oxide, and cobalt then enters blast-furnace cinder, with rich cobalt slag form output.
Because agglomerate contains a small amount of sulphur, a small amount of matte of output, its quantity is no more than 2% of agglomerate weight.Three kinds of products are arranged in the cupola well like this, form three layers because its proportion is different.The bottom is a blister copper, is interrupted with siphon mode and emits, and ingot casting.Matte and slag continuously flow into external crucible by another mouth, further separate, and slag is emitted continuously, casts bulk, and the matte interruption is emitted, and returns sintering.
If out of the ordinary batch of copper zinc cobalt material contains impurity such as plumbous antimony bismuth of arsenic and tin and is above standard, carry out pre-treatment, here can adopt the reversion roasting method, it is with copper zinc cobalt material 47%, low-sulfur vulcanizing agent copper glance 47%, carbonaceous material coke powder 6%, mix by above-mentioned mass percent, low-sulfur vulcanizing agent copper glance preferably copper sulphur mass ratio is greater than 2.Then with ball mill with the material ball mill pulverizing, particle is more in principle, general ball milling just can about 100 orders.Choosing has caking agent again, preferentially selects water here for use, carries out granulation behind the humidification, and as long as particle scale just passable with the stoving oven adaptation, does not have particular requirement in principle, but in order to take into account reaction effect and granulation cost, the control particle diameter is in the 3-6mm scope.Under 800 ℃ of temperature, in the rotary kiln of control nonoxidizing atmosphere, carry out the reversion roasting, the reducing roasting time is controlled at 1.5-2.5 hour scope, preferentially is controlled at 2 hours.The copper zinc cobalt material that the calcining that its roasting is good just uses for new smelting process.
Its chemical process mainly contains:
The arsenic overwhelming majority exists with the cupric arsenate form in the copper zinc cobalt material, and decomposition takes place when roasting for it
Cu
3(AsO
4)
2→3CuO+As
2O
5
Cupric oxide is reduced into copper by carbon or carbon monoxide in the presence of reductive agents such as coke powder
Copper glance decomposites sulphur steam under reducing atmosphere simultaneously, combines with copper to produce stable Cu
2S stops the arsenic of generation subsequently and combining of metallic copper, and arsenic is removed with white arsenic or the volatilization of arsenic steam form.
This method consumption has the reductive agent coke powder, and the vulcanizing agent copper glance of allocating into is the copper raw material of our company, and main consumption is the heavy oil consumption of rotary kiln, so the pre-treatment smelting cost is low.
Pre-treatment also can be adopted wet method, sodium hydroxide solution is flooded copper zinc cobalt material particles, concentration of sodium hydroxide solution is at 120 grams per liters, sodium hydroxide solution and solid materials quality proportioning are 5: 1, extraction time was at 1 hour, extraction temperature adopts three sections adverse current dippings at 90 ℃, and the leached mud that obtains is exactly pretreated copper zinc cobalt material.Simultaneously steeping fluid is reclaimed plumbous zinc of arsenic and saltcake.Its method is that sodium hydroxide solution becomes leach liquor behind dipping copper zinc cobalt material particles, through behind the condensing crystal, Recycling Mother Solution makes and spends dipping copper zinc cobalt material, crystalline mixture is through after water-soluble, replace with calcium hydroxide, here we adopt cheap lime, amount is that the Theoretical Calculation amount is more than three times, make sodium arseniate produce sedimentary Tricalcium arsenate, produce regeneration alkali sodium hydroxide simultaneously, some saltcake also passes and changes regeneration alkali sodium hydroxide into, result's alkali of regenerating rolls up, so after we reclaim Tricalcium arsenate, again the mother liquor condensing crystal is produced saltcake, then debris is gone to wash leached mud and recycle and remove to flood copper zinc cobalt material.Tricalcium arsenate is done pesticide product, and solution can recycle fully, and non discharge sewage reaches the protection of air and water source environment.
Its main chemical reactions process is as follows:
When sodium hydroxide solution dipping copper zinc cobalt material particles, the arsenic in the material mainly is to exist with the cupric arsenate form, with sodium hydroxide generation chemical reaction.
Following chemical reaction takes place when adding lime in steeping fluid.
Thereby produce a large amount of regeneration alkali, make the recycle of raffinate energy, reclaim Tricalcium arsenate simultaneously, do sterilant.
For 1 ton of material pre-treatment, main reagent consumption:
150 kilograms of Ca of NaOH (OH)
2500 kilograms in 80 kilograms of coals
So cost is low, craft science is reasonable, and implements easily.
The technico-economical comparison of the isolating new smelting process of its copper zinc cobalt:
Charge composition:
Agglomerate 100%
Wingdale 15%
Metallurgical coke 18%
Blast furnace specific capacity: 50 tons/meter
2Day
Product composition:
Blister copper Cu94%, Zn4%
Zinc oxide ZnO90%, CdO6%
Rich cobalt slag Co8%,, Cu0.6%, Zn3～5%,
Main subsidiary material consumption:, be amount of metal to producing 1 ton of blister copper
0.5 ton of metallurgical coke
0.4 ton in Wingdale
Metal recovery rate:
Copper recovery 97%
Zinc recovery 90%
The cadmium rate of recovery 92%
The cobalt rate of recovery 94%
Embodiment 2
The used copper zinc of present embodiment cobalt material is low cobalt material, and its chemical ingredients is: Cu25%, Zn25%, Co0.5%, all the other gangue contents and trace element.To the processing of its material, the present invention adopts and obtains rich cobalt slag method indirectly.Because the slag making element is more in the material, it is few to contain the cobalt amount, fails the rich cobalt slag of direct output.Therefore blast furnace adopts higher alkalisation and reducing atmosphere to carry out melting, impels most cobalts to enter in the blister copper, and cobalt reclaims in the oxidation sludge of anode refining in its blister copper, can with the rich cobalt slag of embodiment 1 identical grade.
For keeping blast furnace tuyere zone high temperature, so that zinc oxide is easy to obtain reduction.The high temperature of its tuyere zone reaches to guarantee the slag high-melting-point.Blast furnace is allocated Wingdale into as flux, make basicity of slag
Slag melting is more than 1050 ℃.
Add the carbon containing reducer metallurgical coke, regulate wind material ratio simultaneously and make kiln gas before blasting secondary air
Keep normal reducing atmosphere.
The technico-economical comparison of the isolating new smelting process of its copper zinc cobalt is:
Charge composition:
Agglomerate 100%
Wingdale 20%
Hard coal 20%
Blast furnace specific capacity: 50 tons/meter
2Day
Product composition:
Blister copper Cu90%, Zn1%, Co2.5%
Zinc oxide ZnO90%, CdO 6%
Rich cobalt slag Col2%, Cu2%,
Main subsidiary material consumption:, be amount of metal to 1 ton of blister copper
0.9 ton in hard coal
0.9 ton in Wingdale
Metal recovery rate:
Copper recovery 95%
Zinc recovery 90%
The cobalt rate of recovery 88%
The pre-treatment of copper zinc cobalt material can be adopted pyrogenic process, and mass percent is copper zinc cobalt material 58%, low-sulfur vulcanizing agent copper glance 36%, carbonaceous material coal dust 6%, and maturing temperature is controlled at 700 ℃, and other is as embodiment 1.
The pre-treatment of copper zinc cobalt material also can be adopted wet method, and concentration of sodium hydroxide solution is at 110 grams per liters, and sodium hydroxide solution and solid materials quality proportioning are 7: 1, and extraction time was at 2 hours, and extraction temperature adopts four sections adverse current dippings at 80 ℃, and other is as embodiment 1.
Embodiment 3
The handled material of present embodiment is the copper zinc cobalt material of low zinc, and its chemical ingredients is: Cu30%, Zn10%, Co1.0%, all the other gangue contents and trace element.Because the slag making element is more in this material, though the cobalt contents height, but still fail the satisfied rich cobalt slag of output.Therefore, use the technical qualification identical to obtain rich cobalt slag with embodiment 2.
For keeping blast furnace tuyere zone high temperature, so that zinc oxide is easy to obtain reduction.The high temperature of its tuyere zone reaches to guarantee the slag high-melting-point.Blast furnace is allocated Wingdale into as flux, make basicity of slag
Slag melting is more than 1050 ℃.
Add the carbon containing reducer metallurgical coke, regulate wind material ratio simultaneously and make kiln gas before blasting secondary air
Keep normal reducing atmosphere.
Its technico-economical comparison is:
Charge composition:
Agglomerate 100%
Wingdale 20%
Metallurgical coke 20%
Blast furnace specific capacity: 50 tons/meter
2Day
Product composition:
Blister copper Cu90%, Zn1%, Co3.4%
Zinc oxide ZnO88%
Rich cobalt slag Co18%, Cu2%,
Main subsidiary material consumption:, be amount of metal by producing 1 ton of blister copper
0.7 ton of metallurgical coke
0.7 ton in Wingdale
Metal recovery rate:
Copper recovery 97%
Zinc recovery 85%
The cobalt rate of recovery 92%
The pre-treatment of copper zinc cobalt material can be adopted pyrogenic process, and mass percent is copper zinc cobalt material 36%, low-sulfur vulcanizing agent copper glance 58%, carbonaceous material coke powder 6%, and maturing temperature is controlled at 900 ℃, and other is as embodiment 1.
The pre-treatment of copper zinc cobalt material also can be adopted wet method, and concentration of sodium hydroxide solution is at 130 grams per liters, and sodium hydroxide solution and solid materials quality proportioning are 3: 1, extraction time was at 0.5 hour, extraction temperature adopts three sections adverse current dippings at 95 ℃, and other is as embodiment 1.
Embodiment 4
The handled material of present embodiment is the material of high zinc of high-copper and low cobalt, and its chemical ingredients is: Cu25%, Zn40%, Co0.8%, all the other gangue contents and trace element.Though it is low that this material contains cobalt and since in the material slag making constituent content seldom, it is few to produce the quantity of slag, therefore also can directly obtain rich cobalt slag.But the blast furnace smelting of high zinc material just must have the slag amount of some amount, to keep the blast furnace direct motion.In order not reduce the cobalt grade of rich cobalt slag, blast furnace adopts part slag Returning smelting method to guarantee the rich cobalt slag of output, and its technico-economical comparison is:
Charge composition:
Agglomerate 100%
Wingdale 22%
Refinery coke 25%
Blast furnace specific capacity: 45 tons/meter
2Day
Product composition:
Blister copper Cu93%, Zn5%
Zinc oxide ZnO92%
Rich cobalt slag Co10%, Cu0.6%,
Main subsidiary material consumption:, be amount of metal to producing 1 ton of blister copper
0.9 ton of refinery coke
0.8 ton in Wingdale
Metal recovery rate:
Copper recovery 96%
Zinc recovery 92%
The cobalt rate of recovery 90%
The pre-treatment of copper zinc cobalt material can be adopted pyrogenic process, and mass percent is copper zinc cobalt material 47%, low-sulfur vulcanizing agent copper glance 47%, carbonaceous material coke powder 6%, and maturing temperature is controlled at 800 ℃, and other is as embodiment 1.
The pre-treatment of copper zinc cobalt material also can be adopted wet method, and concentration of sodium hydroxide solution is at 120 grams per liters, and sodium hydroxide solution and solid materials quality proportioning are 5: 1, and extraction time was at 1 hour, and extraction temperature adopts three sections adverse current dippings at 90 ℃, and other is as embodiment 1.
Claims (8)
1, the isolating smelting process of a kind of copper zinc cobalt, it is characterized in that with mass percent being the copper zinc cobalt material of Cu10～50%, Zn10～40%, Co0.2～2.0%, through sintering agglomerate into, be quality criteria then with agglomerate, Wingdale and carbon containing reducer by following quality proportioning with the agglomerate:
Agglomerate 100%
Wingdale 15～22%
Carbon containing reducer 18～25% adds 15～22% Wingdales makes basicity of slag
Guarantee that slag melting more than 1050 ℃, adds 18～25% carbon containing reducer, regulate wind material ratio and make kiln gas before blasting secondary air
To keep normal reducing atmosphere, then these furnace charges blast furnace top of hierarchically packing into, blast furnace bottom blast orifice blasts warm air and carries out melting, furnace roof is provided with overfiren air port and also blasts secondary hot-air, carbon monoxide and zinc fume in the combustion parts furnace gas, keep high temperature furnace roof more than 1000 ℃ by its heat release, to guarantee the smooth and easy discharge of zinc oxide, blast furnace bottom cupola well has three layers of melt, is respectively blister copper, matte and slag, matte and slag continuously flow into external crucible to be separated and emits, matte returns sintering, rich cobalt slag is cast the block cobalt that further reclaims, and blister copper is regularly emitted ingot casting, sends to refining.
2, method according to claim 1 is characterized in that described carbon containing reducer is metallurgical coke, hard coal or refinery coke.
3, method according to claim 1 is characterized in that described agglomerate sulphur content S＜1.5%, piece diameter 30～120mm; Wingdale contains calcium oxide CaO＞50%, piece diameter 30～80mm; Carbon containing reducer carbon content C＞80%, piece diameter 30～80mm.
4, method according to claim 1 is characterized in that described blast furnace is a copper zinc blast furnace, and its stock column remains on 1.8-2.2 rice height, and throat temperature is more than 1000 ℃.
5, method according to claim 1, it is characterized in that the flue gas that described furnace roof is discharged adopts heat exchanger to come preheated air, preheated air uses for air port, bottom and furnace roof overfiren air port, and flue gas reclaims zinc oxide product with bag filter after cooling through surface cooler.
6, method according to claim 1, it is characterized in that described copper zinc cobalt material is through pre-treatment, it with copper zinc cobalt material, low-sulfur vulcanizing agent copper glance, carbonaceous material according to mass percent 36-58%, 36-58%, 2-10% proportioning, mix granulation after the pulverizing, under temperature 700-900 ℃, carry out the reversion roasting then, obtaining calcining is exactly pretreated copper zinc cobalt material, and the main content of its 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％。
7, method according to claim 6 is characterized in that described copper zinc cobalt material, low-sulfur vulcanizing agent copper glance, carbonaceous material proportioning are 46-48%, 4648%, 4-8%; The granulation particle dia is in the 3-6mm size; Granulation is carried out granulation after adopting the water humidification.
8, method according to claim 1, it is characterized in that described copper zinc cobalt material is through pre-treatment, its pre-treatment is to adopt sodium hydroxide solution dipping copper zinc cobalt material particles, concentration of sodium hydroxide solution is at the 110-130 grams per liter, sodium hydroxide solution and solid materials quality proportioning are 3-7: 1, extraction time was at 0.5-2 hour, and extraction temperature is at 80-95 ℃, and leached mud is exactly pretreated copper zinc cobalt material.
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| CN1188533C true CN1188533C (en) | 2005-02-09 |
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| 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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