CN103725896A - Copper-nickel sulfide ore concentrate smelting method through pyrometallurgy - Google Patents
Copper-nickel sulfide ore concentrate smelting method through pyrometallurgy Download PDFInfo
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Abstract
The invention relates to a copper-nickel sulfide ore concentrate smelting method through the pyrometallurgy and particularly relates to improvement of the process for smelting the copper-nickel sulfide ore concentrate through the pyrometallurgy. According to the invention, during the process of transferring smelting slag to a sedimentation electric furnace from a smelting furnace, the reduction slagging reaction of magnetic iron oxide is completed in a chute, so that oxides of nickel, copper and cobalt in the slag are vulcanized and converted into sulphonium. The method provided by the invention has the advantages as follows: the depletion of smelting slag and adjustment of slag types can be completed in the reaction chute, so that the operation of the sedimentation electric furnace is facilitated, and the waste slag discharged from the electric furnace contains less valuable metal, and the metal recovery rate is increased; the smelting slag flows through the reaction chute to adjust the types of slag, so that the smelting slag, which does not contain high magnetic iron oxides or copper-nickel oxides, can be subjected to the smelting process so as to product high-grade sulphonium; the separation of iron and copper nickel is completed during the process of smelting, the blowing of white matte is non-slag smelting, so that the low-air pollution is not caused, and the difficulties of treatment of blowing slag are avoided.
Description
Technical field
A pyrometallurgical smelting method for copper nickel vulcanised ore concentrate, relates to a kind of improvement of technique of pyrometallurgical smelting copper nickel vulcanised ore concentrate.
Background technology
Nonferrous metal sulfide mineral smelting technology is most typical is the smelting of copper sulfide concentrate and nickel sulfide concentrate.From copper sulfide concentrate to blister copper, existing technique is matte smelting in oxygen-enriched air smelting stove, the common copper matte regulus of output (containing Cu45～70%) and smelting slag, the copper matte regulus output blister copper that blows, simultaneously output blowing slag, smelting slag is sent in sedimentation electric furnace with open type chute and is reduced, sulfuration, clarified separation operation, finally discharges the electric furnace slag that cupric is less than 0.5%, some factories also carry out slow cooling, the floating processing of mill to electric furnace slag, to improve the rate of recovery of copper.The blowing quantity of slag is large, also individual curing again.The subject matter that this technical process and equipment configuration exist is: (1) metal recovery rate is low.Owing to adopting oxygen enrichment intensified smelting, in smelting slag, have more martial ethiops, slag character worsens, and in slag, the copper oxide of chemical dissolution is also high, this slag is sent sedimentation electric furnace to, cause electric furnace to occur serious furnace accretion, in sedimentation electric furnace, slag is carried out to reduction-sulfurization processing, but because reacting dynamics condition is poor, adjustment to slag type is limited, in addition electric furnace temperature raising occurs that violent melt stirs, and has disturbed the clarified separation of slag sulfonium, is difficult to obtain the electric furnace waste that cupric is low.Even if adopt slag slow cooling, levigate, flotation processing, can not reclaim the copper component of chemical dissolution; (2) environment protection defectiveness.Common copper matte regulus is bessemerized in slag forming period and is had SO with PS
2low vacancy pollution.If adopt the continuous converting techniques such as top blast blowing or flash blowing, the environment protection of blowing operation is fine, but what produce by boasting is half blister copper that sulfur-bearing is high, and this blister copper will be discharged low concentration SO when pyrorefining
2gas, pollution is transferred.In addition, slag beneficiating method is processed inevitable output fine size, active high powdery mine tailing, and tailings impoundment is all potentially dangerous to atmosphere and underground water.
The smelting of nickel sulfide concentrate, modern crafts flow process is at the low nickel matte of smelting furnace output and smelting slag, low nickel matte is delivered to and is bessemerized with steamed stuffed bun, the high nickel matte of output and blowing slag in converter, high nickel matte is floating through slow cooling mill, separate nickelous sulfide phase, cupric sulfide phase and three products of alloy phase, blowing slag is processed in special slag cleaning furnace.The smelting slag that smelting furnace is discharged is sent in sedimentation electric furnace with open type chute and is reduced, sulfuration, clarified separation operation, and final discharge contains the few electric furnace slag of valuable metal.The subject matter that this technical process and equipment configuration exist is: (1) metal recovery rate is low.Owing to adopting oxygen enrichment intensified smelting, in smelting slag, there are more martial ethiops, magnesium oxide, slag character worsens, in slag, the ambrose alloy cobalt/cobalt oxide of chemical dissolution is also high, the slag that this fusing point is high is sent sedimentation electric furnace to, cause electric furnace to occur serious furnace accretion, effectively settlement space reduces, although slag has been carried out to reduction-sulfurization processing in sedimentation electric furnace, but because reacting dynamics condition is poor, limited to the adjustment of slag type, electric furnace temperature raising occurs that violent melt stirs in addition, disturbed the clarified separation of slag sulfonium, be difficult to obtain containing the low electric furnace waste of valuable metal; (2) the Slag form regulation difficulty of smelting slag.The notable feature of nickel smelting slag type is that MgO is high, causes the fusing point of slag high, and additional more slag formers reduce the accounting of MgO in slag and change the fusing point of slag, and technical is can accomplish but there will be the problem of the large and etch refractory brick of the quantity of slag, and in production, utilization is limited.(3) open type chute has the high drawback of the gentle maintenance cost of the slag of reduction.Nickel smelting slag flows through open type chute and arrives sedimentation electric furnace entrance, and slag temperature drop is low approximately 50 ℃, and for sedimentation electric furnace, dystectic slag temperature declines and makes its operation very difficult.It is all regular toasting in addition chute, cleaning slagging scorification, repairing liner, and manpower and materials have high input.
Summary of the invention
Object of the present invention is exactly the deficiency existing for above-mentioned prior art, provides one to be conducive to the operation of sedimentation electric furnace, and the electric furnace waste of discharge is low containing valuable metal, and metal recovery rate is high; Without low vacancy pollution, obtain the pyrometallurgical smelting method of the rational copper nickel of slag type vulcanised ore concentrate
The object of the invention is to be achieved through the following technical solutions.
A kind of pyrometallurgical smelting method of copper nickel vulcanised ore concentrate, it is characterized in that smelting slag is transferred to from smelting furnace the process of sedimentation electric furnace, in chute, complete the reduction slag making reaction of the martial ethiops in smelting slag, the oxide compound of nickel, copper, cobalt in slag is cured and changes sulfonium into.
The pyrometallurgical smelting method of a kind of copper nickel vulcanised ore concentrate of the present invention, the both walls that it is characterized in that its chute is provided with injection of reducing agent entrance near bottom, chute headwall is provided with smelting slag entrance, slag sulfonium mixture discharge outlet, accident discharging hole, and cold burden input port, smoke outlet, thermometer hole, vision slit are arranged at chute top.
The pyrometallurgical smelting method of a kind of copper nickel vulcanised ore concentrate of the present invention completes dilution and the Slag form regulation of smelting slag in a reduction chute, is beneficial to the operation of sedimentation electric furnace, and the electric furnace waste of discharge is low containing valuable metal, has improved metal recovery rate; Due to smelting slag flow through reduction chute obtain Slag form regulation, do not fear martial ethiops height and the high slag of copper nickel oxide, support melting operation output high-grade matte, at fusion process, just complete the separation of iron and copper nickel, and the blowing of white metal (white matte) is to blow without slag, without low vacancy pollution, avoided again a processing difficult problem for blowing slag.High nickel matte is floating without the direct slow cooling of blowing, mill.Particularly process containing the high nickel sulfide concentrate of magnesium, slag rate is high for the high nickel matte of melting output, and in slag, MgO has obtained dilution, can obtain more rational slag type in sedimentation electric furnace.
The present invention proposes a kind of pyrometallurgical smelting method of copper nickel vulcanised ore concentrate, and its core is two sections of dilution technology, in chute, reduces dilution, then carries out supernatant and separate dilution.
The present invention proposes a kind of pyrometallurgical smelting method of copper nickel vulcanised ore concentrate, in existing oxygen enrichment intensified smelting stove, complete the melting of copper sulfide concentrate or cupric nickel sulfide concentrate, when what process, it is copper sulfide concentrate, the high copper matte regulus of output and cupric is high, containing the high copper smelting slag of martial ethiops, high copper matte regulus is sent into PS converter and is carried out without slag blowing output blister copper.Copper smelting slag reduces dilution, Slag form regulation through reduction chute, then flows into conventional sedimentation electric furnace and carry out supernatant, and the copper matte regulus of carrying secretly in slag is separated, and discharges the electric furnace waste that cupric is less than 0.36%; When what process, be cupric nickel sulfide concentrate, the high nickel matte of output and nickeliferous height, containing the high nickel smelting slag of martial ethiops.High nickel matte carries out after slow cooling, floatation operation, obtains nickel ore concentrate, copper ore concentrates and three products of alloy.Nickel smelting slag reduces dilution, Slag form regulation through reduction chute, then flows into conventional sedimentation electric furnace and carry out supernatant, and the low nickel matte of carrying secretly in slag is separated, and discharges the nickeliferous electric furnace waste that is less than 0.24%.The invention has the advantages that: in a reduction chute, complete dilution and the Slag form regulation of smelting slag, be beneficial to the operation of sedimentation electric furnace, the electric furnace waste of discharge is low containing valuable metal, has improved metal recovery rate; Due to smelting slag flow through reduction chute obtain Slag form regulation, do not fear martial ethiops height and the high slag of copper nickel oxide, support melting operation output high-grade matte, at fusion process, just complete the separation of iron and copper nickel, and the blowing of white metal (white matte) is to blow without slag, without low vacancy pollution, avoided again a processing difficult problem for blowing slag.High nickel matte is floating without the direct slow cooling of blowing, mill.Particularly process containing the high nickel sulfide concentrate of magnesium, slag rate is high for the high nickel matte of melting output, and in slag, MgO has obtained dilution, can obtain more rational slag type in sedimentation electric furnace.
Advantage of the present invention:
1, because reversion agent sprays into from multiple nozzles of lower end, chute both sides, melt has been produced to good stirring, Slag form regulation speed is fast, and the precious metal in slag is had to cleaning function, and can improve rare and scatter element in slag enter dirt rate.
2, technique of the present invention is supported smelting furnace output high-grade matte, can shorten the converting process of sulfonium, and blowing mode is more flexible.
3, sedimentation electric furnace is without bearing reduction-sulfurization function again, as long as supernatant slag just can obtain the waste low containing valuable metal, electric furnace operation is smooth, power consumption is low.
4, avoided smelting slag to be discharged into bonding and the cooling problem in sedimentation electric furnace process through open type chute.
5, for containing the high nickel sulfide concentrate melting of magnesium, slag rate is high to produce high nickel matte, has the effect of MgO in dilution slag, although smelting slag can be higher containing martial ethiops, and after reduction chute reduction-sulfurization, the SiO of low magnesium during sedimentation electric furnace slag belongs to
2-CaO-FeO-MgO quaternary slag, electric furnace slag type is more reasonable.
Accompanying drawing explanation
Fig. 1 adopts the present invention to process the process flow sheet of copper sulfide concentrate;
Fig. 2 adopts the present invention to process the process flow sheet of nickel sulfide concentrate;
Fig. 3 is that reduction chute master of the present invention looks and side-looking structural representation;
Fig. 4 is the side-view of Fig. 3;
Fig. 5 is reduction chute plan structure schematic diagram of the present invention;
Fig. 6 is air nozzle structure figure;
Fig. 7 is reduction chute and bath smelting furnace, sedimentation eaf process device connection diagram.
Embodiment
A pyrometallurgical smelting method for copper nickel vulcanised ore concentrate smelting slag is transferred to from smelting furnace the process of sedimentation electric furnace, completes the reduction slag making reaction of the martial ethiops in smelting slag in chute, and the oxide compound of nickel, copper, cobalt in slag is cured and changes sulfonium into.The both walls of its chute is provided with injection of reducing agent entrance near bottom, and chute headwall is provided with smelting slag entrance, slag sulfonium mixture discharge outlet, accident discharging hole, and cold burden input port, smoke outlet, thermometer hole, vision slit are arranged at chute top.
The concrete steps of copper melting technology of the present invention are:
1, by the copper ore concentrates of cupric 10-35%, quartz and lime stone flux, returning charge, coal drops into smelting furnace with blowing slag by the charge composition of output white metal, and the oxygen material ratio of control is definite by the needs of output white metal, and spray gun inserts Bing Xiang molten bath, molten bath and blasts containing 45%～80% O
2oxygen-rich air, control the Fe/SiO in slag
21.15～1.35, at the temperature of 1150～1250 ℃, carry out melting.
2, in the fusion process of continuous dosing from smelting furnace put sulfonium mouth be interrupted discharge white metal, white metal with steamed stuffed bun handling to bessemerizing.
3, from smelting furnace slag-drip opening, emit continuously the smelting slag entrance (3) of smelting slag to reduction chute, from injection of reducing agent entrance (11), use nozzle (14) by reductive agent and contain oxygen air the ratio spirt chute of pressing coefficient of excess air 0.75～0.85 simultaneously, top of the slag height in maintenance chute is at 1.2～1.5 meters, smelting slag is carried out to Slag form regulation, the flue gas that process produces, by smoke outlet (8) row flue, is released to sedimentation electric furnace through the melt of reduction, sulfuration from slag sulfonium mixture discharge outlet (12).If there is accident, maybe to overhaul chute, open accident discharging hole (13) and discharge melt.The low copper matte regulus of carrying secretly in smelting slag obtains sufficient clarified separation in sedimentation electric furnace, and the low copper matte regulus of emitting from sedimentation electric furnace sulfonium mouth send blowing, and the electric furnace slag that electric furnace slag-drip opening is discharged is stored up as waste through shrend.
The concrete steps of nickel melting technology of the present invention are:
1, by the nickel ore concentrate of nickeliferous 6-8%, copper 3-5%, quartz and lime stone flux, returning charge, coal and blowing slag drop into smelting furnace by the charge composition of the high nickel matte of output (Fe ﹤ 4%), the oxygen material ratio of controlling is definite by the needs of the high nickel matte of output, and spray gun inserts Bing Xiang molten bath, molten bath and blasts containing 45%～80% O
2oxygen-rich air, control the Fe/SiO in slag
21.0～1.25, at the temperature of 1250～1350 ℃, carry out melting.
2, in the fusion process of continuous dosing, from smelting furnace, put sulfonium mouth and be interrupted the handling of the low nickel matte of discharge steamed stuffed bun to bessemerizing, the steamed stuffed bun slow cooling of high nickel matte, slow cooling material send mill floating.
3, from smelting furnace slag-drip opening, emit continuously the smelting slag entrance (3) of smelting slag to reduction chute, from injection of reducing agent entrance (11), use nozzle (14) by reductive agent and contain oxygen air the ratio spirt chute of pressing coefficient of excess air 0.75～0.85 simultaneously, top of the slag height in maintenance chute is at 1.2～1.5 meters, smelting slag is carried out to Slag form regulation, the flue gas that process produces, by smoke outlet (8) row flue, is released to sedimentation electric furnace through the melt of reduction, sulfuration from slag sulfonium mixture discharge outlet (12).If there is accident, maybe to overhaul chute, open accident discharging hole (13) and discharge melt.The low nickel matte of carrying secretly in smelting slag obtains sufficient clarified separation in sedimentation electric furnace, and the low nickel matte of emitting from sedimentation electric furnace sulfonium mouth send blowing, and the electric furnace slag that electric furnace slag-drip opening is discharged is stored up as waste through shrend.
At empty chute, accept first the blow-on stage of smelting slag, need to discharge the smelting slag that contains appropriate raw material to reduction chute from smelting furnace, slag input is on one side reduction on one side, this kind of smelting slag reverted to 1 meter high of the chute top of the slag, slag and containing martial ethiops, be less than 3%, meet this condition and just can discharge continuously the slag that refines high nickel matte to chute from smelting furnace.
Newly-increased one section of dilution principle comprises: 1) use thermal insulation chute winding-up reductive agent, reach strengthening reduction object; 2) utilize the chute discrepancy in elevation to reach dynamic reduction effect.
4, the low nickel matte of separating from sedimentation electric furnace is with bessemerizing into high nickel matte, and blowing slag turns back to smelting furnace.
Reduction chute is by refractory brick bottom land (1), close-fitting hoop (2), copper water jacket hook 3), smelting slag import (4), cell body side water jacket (5), groove top water jacket (6), cold burden adds entrance (7), thermometer hole (8), flue (9), vision slit (10), cell body side copper water jacket (11), injection of reducing agent entrance (12), cell body end water jacket (13), slag sulfonium mixture discharge outlet (14), accident discharging hole (15), reductant nozzle (16) composition, wherein nozzle is by primary air and fine coal entrance (17), secondary air entrance (18), ball valve (19) forms.Replace open type chute with this reduction chute, in the transfer process of smelting slag just to slag in Fe3O4 reduce, the oxide compound of the Cu, Ni and Co in slag is vulcanized, simultaneously, control the ratio of reductive agent and oxygen, allow the reaction of partial reduction agent generation incomplete combustion that heat is provided, maintain slag temperature.
For further illustrating the present invention, provide the embodiment of following indefiniteness.
Embodiment 1
On traditional matte smelting technique basis, copper ore concentrates and flux, returning charge, blowing slag are mixed in proportion, join in smelting furnace continuously, and fill into appropriate coal as fuel, under excess oxygen, melting generates white matte.
Copper ore concentrates composition used (%) is:
The hard coal composition that fuel adopts is:
Press iron-holder and the contained SiO of furnace charge of copper ore concentrates
2mass ratio=1: 0.9 adds quartzy batching.In the melting operation operation of top blast stove (4 meters of internal diameters, burner hearth high 13.6 meters), (add-on per hour) adds 60 tons of copper ore concentratess and 1.2 tons of flue dust (containing Cu8%), 0.3 ton of blowing slag (containing Cu4%, Fe
3o
437%), add hard coal, the 18000N m of 2.5 tons simultaneously
3oxygen concn is that the quartzite of 68% oxygen-rich air and 7 tons is (containing SiO
280%).Oxygen-rich air sprays into molten bath with oxygen rifle from furnace roof, controls the temperature of melt in stove at 1150 ℃～1220 ℃.Employing is interrupted the system (discharge matte wants interval just to enter discharge next time for 40 minutes 20 minutes) of emitting matte from slag notch continuous discharging slag with from the escape orifice of matte, and the white matte composition that melting generates is: Cu 78%, Fe 0.5%, S 20.2%.
34 tons of smelting slags of discharge per hour are to reduction chute.Reduction chute parameter and operational indicator:
Bottom land internal area: 3.9m
2;
Interior dimensions: long × wide × high (m): 3.25 × 1.2 × 3.5;
Air port number: 8,4 of every sides;
Reduction consumption of coal amount: 4.42 tons/h;
Pressurized air unit consumption: 14700Nm
3/ h;
The slag sulfonium mixture of sending sedimentation electric furnace to from chute is through clarified separation, and electric furnace waste is containing Cu 0.36%.
Embodiment 2
On traditional nickel melting technology basis, nickel ore concentrate and flux, returning charge, blowing slag are mixed in proportion, join in smelting furnace continuously, and fill into appropriate coal as fuel, under excess oxygen, melting generates high nickel matte.
Nickel ore concentrate composition used (%) is:
| Element | Ni | Cu | Co | Fe | S | SiO 2 | CaO | MgO |
| Content | 6.36 | 3.69 | 0.2 | 31.34 | 25.36 | 11.2 | 2.55 | 6.94 |
The hard coal composition that fuel adopts is:
| Composition | Fixed carbon | Volatile matter | Ash content | Add up to |
| % | 75.00 | 10.00 | 15.00 | 100.00 |
Press iron-holder and the contained SiO of furnace charge of nickel ore concentrate
2mass ratio=1: 1 adds quartzy batching.In the melting operation operation of horizontal oxygen side blown converter (3.7 × 16.7 meters of stove specification Φ), 35 tons of nickel ore concentrates and 1.4 tons of flue dust (containing Ni 4.88%, Cu 4.12%), the 0.2 ton of blowing slag of adding per hour (contains Cu 0.98%, Ni 1.97%, Fe
3o
421%), add hard coal, the 9000Nm of 2.45 tons simultaneously
3oxygen concn is that the quartzite of 60% oxygen-rich air and 8.8 tons is (containing SiO
280%).Oxygen-rich air sprays into molten bath with oxygen rifle from body of heater sidepiece air port, controls the temperature of melt in stove at 1250 ℃～1320 ℃.Employing is interrupted the system (discharging high nickel matte wants interval just to enter discharge next time for 45 minutes 15 minutes) of emitting high nickel matte from slag notch continuous discharging slag with from sulfonium mouth, and the high nickel matte composition that melting generates is: Ni 42.06%, Cu 24.15%, Fe3.16%, Co 0.69%, S 24.7%.
29.7 tons of smelting slags of discharge per hour are to reduction chute.Reduction chute parameter and operational indicator:
Bottom land internal area: 5.28m
2;
Interior dimensions: long × wide × high (m): 4.4 × 1.2 × 3.5;
Air port number: 10,5 of every sides;
Reduction consumption of coal amount: 4.6 tons/h;
Pressurized air unit consumption: 15360Nm
3/ h;
The slag sulfonium mixture of sending sedimentation electric furnace to from chute is through clarified separation, and electric furnace waste is containing Ni 0.24%, Cu 0.19%, Co 0.08%.
Claims (2)
1. the pyrometallurgical smelting method of a copper nickel vulcanised ore concentrate, it is characterized in that smelting slag is transferred to from smelting furnace the process of sedimentation electric furnace, in chute, complete the reduction slag making reaction of the martial ethiops in smelting slag, the oxide compound of nickel, copper, cobalt in slag is cured and changes sulfonium into.
2. the pyrometallurgical smelting method of a kind of copper nickel vulcanised ore concentrate according to claim 1, the both walls that it is characterized in that its chute is provided with injection of reducing agent entrance near bottom, chute headwall is provided with smelting slag entrance, slag sulfonium mixture discharge outlet, accident discharging hole, and cold burden input port, smoke outlet, thermometer hole, vision slit are arranged at chute top.
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| CN104232911A (en) * | 2014-09-30 | 2014-12-24 | 济源市欣欣实业有限公司 | Method for producing white matte by mixed smelting of copper refining slags-pyrite-bornite tailings |
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| CN109477160A (en) * | 2016-07-22 | 2019-03-15 | 奥图泰(芬兰)公司 | The method for refining copper sulfide concentrate |
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