CN113201653A - Dilution-side-top composite converting and reducing integrated method for molten copper slag - Google Patents
Dilution-side-top composite converting and reducing integrated method for molten copper slag Download PDFInfo
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- CN113201653A CN113201653A CN202110467927.6A CN202110467927A CN113201653A CN 113201653 A CN113201653 A CN 113201653A CN 202110467927 A CN202110467927 A CN 202110467927A CN 113201653 A CN113201653 A CN 113201653A
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- slag
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- depletion
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- 239000002893 slag Substances 0.000 title claims abstract description 140
- 239000010949 copper Substances 0.000 title claims abstract description 127
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 126
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 title claims description 5
- 238000006722 reduction reaction Methods 0.000 claims abstract description 103
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000001301 oxygen Substances 0.000 claims abstract description 68
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 68
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000007664 blowing Methods 0.000 claims abstract description 48
- 239000000446 fuel Substances 0.000 claims abstract description 38
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 37
- 239000007921 spray Substances 0.000 claims abstract description 31
- 238000010907 mechanical stirring Methods 0.000 claims abstract description 26
- 229910052742 iron Inorganic materials 0.000 claims abstract description 24
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 23
- 238000010790 dilution Methods 0.000 claims abstract description 17
- 239000012895 dilution Substances 0.000 claims abstract description 17
- 238000003723 Smelting Methods 0.000 claims abstract description 8
- 230000000779 depleting effect Effects 0.000 claims abstract description 5
- 238000002347 injection Methods 0.000 claims abstract description 4
- 239000007924 injection Substances 0.000 claims abstract description 4
- 238000007599 discharging Methods 0.000 claims abstract 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000003245 coal Substances 0.000 claims description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003546 flue gas Substances 0.000 claims description 6
- 229910052683 pyrite Inorganic materials 0.000 claims description 6
- 239000003345 natural gas Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000003034 coal gas Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 235000019738 Limestone Nutrition 0.000 claims description 3
- 239000000571 coke Substances 0.000 claims description 3
- 238000004939 coking Methods 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 3
- 239000006028 limestone Substances 0.000 claims description 3
- 229910052960 marcasite Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims description 3
- 239000011028 pyrite Substances 0.000 claims description 3
- 238000004857 zone melting Methods 0.000 claims description 3
- 229910001018 Cast iron Inorganic materials 0.000 claims description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002802 bituminous coal Substances 0.000 claims description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 2
- 239000003610 charcoal Substances 0.000 claims description 2
- 238000002485 combustion reaction Methods 0.000 claims description 2
- 239000010436 fluorite Substances 0.000 claims description 2
- 239000003517 fume Substances 0.000 claims description 2
- 239000004571 lime Substances 0.000 claims description 2
- 238000011946 reduction process Methods 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- 230000001502 supplementing effect Effects 0.000 claims description 2
- 238000005496 tempering Methods 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 238000003756 stirring Methods 0.000 abstract description 10
- 239000007789 gas Substances 0.000 abstract description 9
- 238000002844 melting Methods 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 6
- 230000008018 melting Effects 0.000 abstract description 5
- 238000005507 spraying Methods 0.000 abstract description 5
- 239000002918 waste heat Substances 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 description 5
- 239000013589 supplement Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000001698 pyrogenic effect Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000003113 dilution method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/0006—Making spongy iron or liquid steel, by direct processes obtaining iron or steel in a molten state
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/0066—Preliminary conditioning of the solid carbonaceous reductant
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
- C22B15/0028—Smelting or converting
- C22B15/0052—Reduction smelting or converting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention relates to a dilution-side-top combined blowing, melting and reduction integrated method for molten copper slag, and belongs to the field of comprehensive utilization of copper slag. The method comprises the following specific steps: (1) adding molten copper slag into a dilution smelting zone through a feeding port, and blowing oxygen-enriched fuel to heat the copper slag; (2) adding a depleting agent into the molten copper slag through a depleting agent feeding port, carrying out vortex depletion under the action of a vortex formed by mechanical stirring or gas injection stirring, and discharging depleted matte from a copper matte outlet and returning the matte to a copper smelting main flow; (3) the depleted slag overflows to a reduction zone, then a slagging agent and a reducing agent are added into a depleted slag molten pool, meanwhile, an oxygen-enriched fuel is sprayed through a top spray gun, CO for melting reduction is combusted, the temperature of the molten pool is raised to maintain thermal balance, and eddy current melting reduction is carried out under the action of mechanical stirring or gas spraying stirring; (4) and the copper-containing molten iron obtained by reduction is discharged from a molten iron outlet, and the reducing slag is discharged from a slag outlet. The invention provides a new idea of a dilution-side-top combined converting and reducing integrated method for molten copper slag, which can realize high-efficiency recovery of valuable components of copper and iron in the copper slag, high-valued slagging-free 100% utilization and cooperative utilization of copper slag waste heat.
Description
Technical Field
The invention relates to the field of comprehensive utilization of copper slag, in particular to a dilution-side-top combined converting and reducing integrated method for molten copper slag, and particularly relates to a resource high-value and waste heat synergistic utilization method for thermal-state copper slag.
Background
The smelting slag generated by oxygen-enriched blowing has high copper content, and the dilution and copper recovery treatment of the copper slag is required. At present, the dilution and recovery of copper are mainly carried out by a slow cooling beneficiation method and a pyrogenic dilution smelting method. The beneficiation method can realize good copper capture, recover most of the impurity matte, but cannot realize the utilization of tailings. The pyrogenic process dilution is carried out by carrying out electric heating dilution on thermal state slag, and the copper-containing slag is put into a dilution furnace for sedimentation and slag matte separation reduction, wherein the copper content of the slag is generally below 0.4-0.5%. But the vulcanizing agent in the pyrogenic process dilution process is seriously volatilized and seriously pollutes the environment, the vulcanizing agent floats on the surface of the molten slag and is difficult to be fully contacted with a molten slag pool, and the utilization rate of the vulcanizing agent is low. In the existing fire-method depletion process, the residual content of copper in the depleted slag is about 0.5 percent, and the recovery rate of copper is low.
Relevant domestic researchers have carried out a large amount of research work on the comprehensive utilization of copper slag, for example, patent CN201910987438.6 discloses a method for producing zinc oxide and ferrosilicon alloy by using copper slag, which can realize the separation of ferrosilicon powder and copper slag, and patent CN201811038730.5 discloses a method for preparing metallic iron by using copper slag, which comprises the following steps: carrying out alkaline process on copper slag, and carrying out vulcanization separation to obtain a sulfonium phase and a slag phase, wherein copper and FeO are enriched in the sulfonium phase, and As is enriched in the slag phase; and then carrying out melting reduction separation on the matte phase to realize the separation of the iron and the matte phase so as to obtain molten metal, wherein copper is reserved in the matte phase. The existing methods can realize the recovery and utilization of iron and other components in the copper slag, but the treatment process of the tailings cannot realize non-slagging and clean treatment. Meanwhile, the copper slag is possibly in a high-temperature state when discharged from the furnace, the sensible heat of the copper slag cannot be utilized in the methods, and the problem of low energy utilization rate exists.
Disclosure of Invention
The invention provides a new idea of a dilution-side-top combined converting and reducing integrated method for molten copper slag, which can realize high-efficiency recovery of valuable components of copper and iron in the copper slag, high-valued slagging-free 100% utilization and cooperative utilization of copper slag waste heat.
The method for realizing the invention comprises the following steps:
the dilution-side top combined converting and reducing integrated method for the molten copper slag comprises the following steps of:
(1) feeding molten copper slag into the depletion region through a molten copper slag feeding port, and blowing oxygen-enriched fuel (such as pulverized coal, coal gas or a mixture of natural gas and oxygen) through a fuel spray gun at the side part of the depletion region to heat the molten copper slag to form a depletion region molten pool and maintain the temperature of the depletion region molten pool; the combustion of the oxygen-enriched fuel blown from the side can raise the temperature of the melting pool in the dilution zone to maintain the heat balance of the system, and the dilution temperature is controlled to be 1250-1350 ℃.
(2) The barren agent is added into a barren zone molten pool through a barren agent feed inlet for carrying out vortex barren, barren generates copper matte and barren slag, and the copper matte is discharged and recycled through a copper matte outlet. The vortex flow of the depletion region can be generated by side blowing of a fuel spray gun, and preferably, a mechanical stirring paddle can be arranged in the depletion region to further strengthen the vortex flow, and the mechanical stirring paddle of the depletion region is arranged at the interface of a copper slag layer and a depletion slag layer of a molten pool in the depletion region when the depletion reaction is carried out and rotates at the speed of 5rpm-100 rpm.
Taking the FeS barrenner as an example, the main reactions occurring in the process of barrenness of molten copper slag are:
Cu2O+FeS＝Cu2S+FeO
3Fe3O4+FeS+5SiO2＝5(2FeO·SiO2)+SO2
(3) and (3) overflowing the depleted slag to a reduction zone, spraying oxygen-enriched fuel to a reduction molten pool through a top-blowing spray gun at the top of the reduction zone, spraying oxygen-enriched air through a side-blowing spray gun at the side of the reduction zone, fully burning CO generated by reduction to supplement heat and raise temperature of the molten pool, and maintaining the heat balance of the system, wherein the reduction temperature is 1450-1550 ℃. And adding a reducing agent and a slag former into the reduction zone melting pool for eddy current reduction, wherein the reducing agent and the slag former can be added from a solid charging port, or the reducing agent and the slag former are carried by using the gas sprayed by side blowing as carrier gas and are sprayed into the reduction zone melting pool by side blowing. The addition amount of the reducing agent is added according to 1.0-1.5 times of the molar content of oxygen in the depleted slag ferrous oxide, and the slagging agent is added according to the binary basicity of the slag, namely 1.0-1.4. Taking a coking coal reducing agent as an example, the main reaction in the reduction process is as follows:
C+CO2＝2CO
Fe3O4+4CO＝3Fe+4CO2
FeO+CO＝Fe+CO2
Cu2O+CO＝2Cu+CO2
similar to the depletion region, the vortex of the vortex reduction is generated by gas blowing stirring, and preferably, a mechanical stirring paddle can be arranged in the reduction region to further strengthen the vortex, and the mechanical stirring paddle in the reduction region is arranged at the slag-metal interface of a molten pool in the reduction region when the reduction reaction is carried out and rotates at the speed of 5rpm-100 rpm.
(4) The copper-containing molten iron obtained by reduction is discharged from a molten iron outlet and can be used for smelting copper-containing steel or copper-containing cast iron; reducing slag is discharged from a slag outlet, and high-temperature tempering can be directly carried out for resource utilization.
Preferably, the lead and zinc are recovered by fume during the vortex depletion and the vortex reduction.
Preferably, the oxygen-enriched fuel is pulverized coal, coal gas or a mixture of natural gas and oxygen, and the oxygen content (mass) is preferably more than 30%; oxygen-enriched air is air with an oxygen content of more than 21%. .
Preferably, the depleting agent may be FeS or FeS2One or more of pyrite, copper concentrate and carbonaceous leaner, wherein the reducing agent can be one or more of carbonaceous reducing agents such as coke, charcoal, bituminous coal and coking coal, and the slagging agent can be CaO and CaF2One or more of lime, limestone and fluorite.
Compared with the traditional copper slag comprehensive utilization process, the method has the following technical advantages and innovations:
(1) the injection of the oxygen-enriched fuel is adopted to carry out temperature rise dilution smelting treatment on the molten copper slag, so that the high-efficiency low-energy consumption temperature rise smelting treatment on the copper slag is realized, and the waste heat of the copper slag is effectively utilized.
(2) The invention realizes the integration of dilution and reduction and has low equipment investment.
(3) The device adopts oxygen-enriched top-blown heat supplement, fully burns CO gas and reduces reduction energy consumption.
(4) The invention adopts the means of side-top composite blowing, vortex dilution and the like, realizes the efficient addition and the efficient dispersion distribution of the barrenner, the reducing agent and the slagging agent, and improves the efficiency of vortex dilution and reduction reaction.
(5) The reduced slag obtained after the reduction of the barren slag can be directly subjected to high-temperature quality control and cooling control, products such as cement clinker and the like can be directly obtained, and the slag-free resource utilization of the copper slag is realized.
Description of the drawings:
FIG. 1 is a schematic view of a copper slag depletion-side top combined converting and reducing integrated furnace adopted in the embodiment of the invention.
Reference numerals: 1-melting a copper slag feed inlet; 2-a feeding port of the lean agent; 3-a fuel lance; 4-mechanical stirring paddles in the depletion zone; 5-a depletion zone flue gas outlet; 6-upper retaining wall; 7-a solid feed port; 8-top-blown spray gun; 9-mechanical stirring paddle in reduction zone; 10-a reduction zone flue gas outlet; 11-a slag outlet; 12-molten iron outlet; 13-side-blown spray gun; 14-lower retaining wall; 15-copper matte outlet.
Detailed Description
The copper slag adopted by the embodiment of the invention comprises the following main components:
the pulverized coal adopted by the embodiment of the invention comprises the following main components: 69.17% of fixed carbon, 11.13% of ash and 19.42% of volatile components. The pulverized coal and the oxygen are mixed to form the oxygen-enriched fuel.
The barretter FeS adopted in the embodiment of the invention2The main components of the composition are as follows: FeS297% and the balance being mainly SiO2。
The reducing agent coke adopted by the embodiment of the invention comprises the following main components: fixed carbon 80.17%, the rest components are ash and volatile matter.
The slag former adopted by the embodiment of the invention is as follows: limestone, wherein CaCO3The content is more than 90 percent.
The production content of the invention is not limited to the raw materials, and natural gas and the like can be used for replacing the fuel. FeS was used as the depleting agent in this example2FeS, pyrite, copper concentrates or carbonaceous leaners may also be used.
The device adopted by the embodiment of the invention is shown in figure 1, and the furnace body is a horizontal furnace body and comprises a depletion area of the furnace body and a reduction area of the furnace body. And a retaining wall is arranged between the furnace body depletion area and the furnace body reduction area, the top of the retaining wall (namely, an upper retaining wall 6) is connected with the top of the furnace body, the bottom of the retaining wall (namely, a lower retaining wall 14) is connected with the bottom of the furnace body, a channel is arranged in the middle of the retaining wall, and the depletion slag in the furnace body depletion area can pass through the overflow through channel and enter the furnace body reduction area.
The impoverishment system of the copper slag impoverishment-side top composite converting and reducing integrated furnace comprises a furnace body impoverishment area, a molten copper slag feed inlet 1, a fuel spray gun 3, a impoverishment agent feed inlet 2, an impoverishment area flue gas outlet 5, an impoverishment area mechanical stirring paddle 4 and a copper matte outlet 15. The molten copper slag feed inlet 1 is arranged above the end part of one end of the impoverishment area of the furnace body, the impoverishment agent feed inlet 2 and the impoverishment area flue gas outlet 5 are arranged at the top of the impoverishment area of the furnace body, the mechanical stirring paddle 4 of the impoverishment area is arranged inside the impoverishment area of the furnace body, and the copper matte outlet 15 is arranged at the lower part of the impoverishment area of the furnace body.
The reduction system of the copper slag depletion-side top combined converting and reducing integrated furnace comprises a furnace body reduction area, a solid feeding port 7 and a reduction area smoke outlet 10 which are arranged at the top of the furnace body reduction area, an oxygen-enriched blowing system, a slag outlet 11 and a molten iron outlet 12 which are arranged at one end part of the furnace body reduction area, and a reduction area mechanical stirring paddle 9 in the furnace body reduction area, wherein the oxygen-enriched blowing system comprises a top-blowing spray gun 8 arranged at the top of the furnace body reduction area and a side-blowing spray gun 13 arranged at the side part of the furnace body reduction area.
Example 1:
(1) adding molten copper slag into a depletion region through a molten copper slag feed opening 1, laterally blowing oxygen-enriched fuel consisting of pulverized coal and oxygen with the oxygen content of more than 30% through a fuel spray gun 3 at the side part of the depletion region, heating the molten copper slag to 1300 ℃ to form a depletion region molten pool, and maintaining the temperature of the depletion region molten pool;
(2) the barren agent is added into a barren zone molten pool from a barren agent feed inlet 2 for carrying out vortex barren, the rotating speed of a barren zone mechanical stirring paddle 4 is 100rpm, and the barren time is 30 min; the copper matte and the depleted slag containing 0.48 percent of copper are generated by depletion, and the copper matte is discharged and recycled from a copper matte outlet 15;
(3) the lean slag overflows to a reduction zone, oxygen-enriched fuel is sprayed into a reduction molten pool through a top-blowing spray gun 8 at the top of the reduction zone, the oxygen-enriched fuel mixed by pulverized coal and oxygen and CO generated by reduction are fully combusted to supplement heat and raise the temperature of the molten pool, and the temperature of the reduction molten pool is raised and maintained at 1500 ℃; adding a slagging agent into a reduction molten pool from a solid feeding port 7 under the vortex stirring action of a mechanical stirring paddle 9 in a reduction region, then spraying a reducing agent and oxygen-enriched air with the oxygen content of 50% into the molten pool through a side-blowing spray gun 13, and carrying out vortex reduction under the actions of gas blowing and mechanical vortex stirring, wherein the rotating speed of the mechanical stirring paddle 9 in the reduction region is 100rpm, and the reduction time is 60 min; the adding amount of the reducing agent is added according to 1.3 times of the oxygen molar content in the depleted slag ferrous oxide, and the slagging agent is added according to the slag alkalinity of 1.2;
(4) the molten iron containing 1.05% of copper obtained by reduction is discharged from a molten iron outlet 12; the reducing slag is discharged from the slag outlet 11.
Example 2:
(1) adding molten copper slag into a depletion region through a molten copper slag feed opening 1, blowing oxygen-enriched fuel consisting of pulverized coal and oxygen with the oxygen content of more than 50% through a fuel spray gun 3 at the side part of the depletion region, heating the molten copper slag to 1350 ℃ to form a depletion region molten pool, and maintaining the temperature of the depletion region molten pool;
(2) the barren agent is added into a barren zone molten pool from a barren agent feed inlet 2 for vortex barren, the rotating speed of a barren zone mechanical stirring paddle 4 is 80rpm, and the barren time is 30 min. The copper matte and the depleted slag containing 0.39 percent of copper are generated by depletion, and the copper matte is discharged and recycled from a copper matte outlet 15;
(3) the lean slag overflows to a reduction zone, oxygen-enriched fuel is sprayed into a reduction molten pool through a top-blowing spray gun 8, oxygen-enriched air with the oxygen content of 50% is sprayed through a side-blowing spray gun 13, the oxygen-enriched fuel and CO generated by reduction are fully combusted to perform heat supplementing and temperature rise on the molten pool, and the temperature rise is performed and the temperature of the reduction molten pool is maintained at 1550 ℃; adding a slagging agent and a reducing agent into a reduction molten pool from a solid feeding port 7 under the vortex stirring action of a mechanical stirring paddle 9 in a reduction region, and carrying out vortex reduction under the actions of gas blowing and mechanical vortex stirring, wherein the rotating speed of the mechanical stirring paddle 9 in the reduction region is 80rpm, and the reduction time is 50 min; the adding amount of the reducing agent is added according to 1.4 times of the oxygen molar content in the depleted slag ferrous oxide, and the slagging agent is added according to the slag alkalinity of 1.3;
(4) the molten iron containing 0.87% of copper obtained by reduction is discharged from a molten iron outlet 12; the reducing slag is discharged from the slag outlet 11.
Example 3
(1) Adding molten copper slag into a depletion region through a molten copper slag charging port 1, blowing oxygen-enriched fuel consisting of coal gas and oxygen with the oxygen content of 60% through a fuel spray gun 3 at the side part of the depletion region, heating the molten copper slag to 1250 ℃ to form a depletion region molten pool, and maintaining the temperature of the depletion region molten pool;
(2) the barren agent is added into a barren zone molten pool from a barren agent feed inlet 2 for vortex barren, the rotating speed of a barren zone mechanical stirring paddle 4 is 20rpm, and the barren time is 40 min. The copper matte and the depleted slag containing 0.42 percent of copper are generated by depletion, and the copper matte is discharged and recycled from a copper matte outlet 15;
(3) the lean slag overflows to a reduction zone, oxygen-enriched fuel is sprayed into a reduction molten pool through a top-blowing spray gun 8, oxygen-enriched air with the oxygen content of 50% is sprayed through a side-blowing spray gun 13, the oxygen-enriched fuel and CO generated by reduction are fully combusted to supplement heat and raise the temperature of the molten pool, and the temperature is raised and the temperature of the reduction molten pool is maintained at 1450 ℃; spraying a reducing agent, a slagging agent and oxygen-enriched air with the oxygen content of 50% into the molten bath through a side-blowing spray gun 13, and carrying out eddy reduction under the actions of gas blowing and mechanical eddy stirring, wherein the rotating speed of a mechanical stirring paddle 9 in a reduction zone is 10rpm, and the reduction time is 40 min; the adding amount of the reducing agent is added according to 1.0 time of the oxygen molar content in the depleted slag ferrous oxide, and the slagging agent is added according to the slag alkalinity of 1.4;
(4) the molten iron containing 0.80% of copper obtained by reduction is discharged from a molten iron outlet 12; the reducing slag is discharged from the slag outlet 11.
Example 4
(1) Adding molten copper slag into a depletion region through a molten copper slag feeding port 1, blowing oxygen-enriched fuel consisting of natural gas and oxygen with the oxygen content of 40% through a fuel spray gun 3 at the side part of the depletion region, heating the molten copper slag to 1300 ℃ to form a depletion region molten pool, and maintaining the temperature of the depletion region molten pool;
(2) the barren agent is added into a barren zone molten pool from a barren agent feed inlet 2 for vortex barren, the rotating speed of a barren zone mechanical stirring paddle 4 is 60rpm, and the barren time is 50 min. The copper matte and the depleted slag containing 0.44 percent of copper are generated by depletion, and the copper matte is discharged and recycled from a copper matte outlet 15;
(3) the lean slag overflows to a reduction zone, oxygen-enriched fuel is sprayed into a reduction molten pool through a top-blowing spray gun 8, oxygen-enriched air with the oxygen content of 50% is sprayed through a side-blowing spray gun 13, the oxygen-enriched fuel and CO generated by reduction are fully combusted to supplement heat and raise the temperature of the molten pool, and the temperature is raised and maintained at 1480 ℃; a reducing agent is added into a reduction molten pool from a solid feeding port 7 in the reduction zone under the vortex stirring action of a mechanical stirring paddle 9, then a slag former and oxygen-enriched air with the oxygen content of 50% are sprayed into the molten pool through a side-blowing spray gun 13, vortex reduction is carried out under the actions of gas blowing and mechanical vortex stirring, the rotating speed of the mechanical stirring paddle 9 in the reduction zone is 50rpm, and the reduction time is 60 min; the adding amount of the reducing agent is added according to 1.5 times of the oxygen molar content in the depleted slag ferrous oxide, and the slag-forming agent is added according to the slag alkalinity of 1.0;
(4) the molten iron containing 0.95% of copper obtained by reduction is discharged from a molten iron outlet 12; the reducing slag is discharged from the slag outlet 11.
Claims (10)
1. A dilution-side top composite converting and reducing integrated method for molten copper slag is characterized in that:
the blowing and reducing integrated furnace is adopted for carrying out the blowing and reducing integrated furnace, the blowing and reducing integrated furnace comprises a depletion system and a reducing system, and the depletion system and the reducing system are connected in series; the furnace body of the blowing and reducing integrated furnace is a horizontal furnace body, and the furnace body comprises a depletion area and a reducing area; the dilution system comprises a dilution zone, a molten copper slag feed inlet, a fuel injection system, a leaner feed inlet, a dilution zone flue gas outlet and a copper matte outlet, wherein the fuel injection system is a fuel spray gun arranged at the side part of the dilution zone; the reduction system comprises a reduction zone, a solid charging port, a reduction zone flue gas outlet, an oxygen-enriched blowing system, a slag outlet and a molten iron outlet, wherein the oxygen-enriched blowing system comprises a top-blowing spray gun arranged at the top of the reduction zone and a side-blowing spray gun arranged at the side part of the reduction zone; a retaining wall is arranged between the depletion region and the reduction region, the top of the retaining wall is connected with the top of the furnace body, the bottom of the retaining wall is connected with the bottom of the furnace body, a channel is arranged in the middle of the retaining wall, and depletion slag in the depletion region can pass through the channel through overflow and enter the reduction region;
the dilution-side top combined converting and reducing integrated method for the molten copper slag comprises the following steps of:
(1) adding molten copper slag into a depletion region from a molten copper slag feed inlet, and blowing oxygen-enriched fuel through a fuel spray gun at the side of the depletion region to heat the molten copper slag to form a depletion region molten pool and maintain the temperature of the depletion region molten pool;
(2) the barren agent is added into a barren zone molten pool through a barren agent feed inlet for carrying out vortex barren, barren copper matte and barren slag are generated through barren, and the copper matte is discharged and recycled through a copper matte outlet;
(3) the lean slag overflows to a reduction zone, oxygen-enriched fuel is injected into a reduction molten pool through a top-blowing spray gun at the top of the reduction zone, oxygen-enriched air is injected through a side-blowing spray gun at the side part of the reduction zone, and CO generated by full combustion and reduction is used for supplementing heat and raising the temperature of the molten pool; adding a reducing agent and a slagging agent into a reduction zone melting pool for eddy current reduction;
(4) discharging the copper-containing molten iron obtained by reduction from a molten iron outlet; the reducing slag is discharged from a slag outlet.
2. The integrated molten copper slag depletion-side and top combined converting and reducing process as claimed in claim 1, wherein the depletion zone and the reduction zone are respectively provided with mechanical stirring paddles, the mechanical stirring paddles of the depletion zone are arranged at the interface of the copper slag layer and the depletion slag layer of the molten pool of the depletion zone when the depletion reaction is carried out, the mechanical stirring paddles of the reduction zone are arranged at the interface of the slag layer and the metal layer of the molten pool of the reduction zone when the reduction reaction is carried out, and the rotating speed of the mechanical stirring paddles of the depletion zone and the reduction zone is 5rpm-100 rpm.
3. The integrated molten copper slag depletion-side-top combined converting and reducing method of claim 1, characterized in that the depletion zone adopts side-blown oxygen-enriched fuel to raise the temperature of the depletion zone molten pool and maintain the heat balance of the system, and the depletion temperature is 1250-1350 ℃.
4. The depleted-side-top combined converting and reducing integrated method of the molten copper slag as claimed in claim 1, wherein the reduction zone adopts a top blowing mode to blow oxygen-enriched fuel to a reduction zone molten pool for raising the temperature and maintaining the system heat balance, and the reduction temperature is 1450-1550 ℃.
5. The integrated process of depletion and side-top combined converting and reducing of molten copper slag as claimed in claim 1, wherein the method for adding the reducing agent and the slag-forming agent into the reduction zone molten pool in the step (3) is as follows: reducing agent and slag former are added from a solid charging port or are blown into the reduction zone molten bath by side blowing through a side blowing spray gun at the side part of the reduction zone.
6. The integrated process of depletion-side-top combined converting and reducing of molten copper slag according to claim 1, wherein the molten iron containing copper obtained by reduction is discharged from a molten iron outlet and used for smelting copper-containing steel or copper-containing cast iron; and discharging the reducing slag from a slag outlet, and directly carrying out high-temperature tempering for resource utilization.
7. The integrated molten copper slag depletion-side-top combined converting and reducing process according to claim 1, characterized in that lead and zinc are recovered by fume during the vortex depletion and the vortex reduction.
8. The integrated molten copper slag depletion-side-top combined converting and reducing process of claim 1, wherein the oxygen-enriched fuel is pulverized coal, coal gas or a mixture of natural gas and oxygen with an oxygen content of more than 30%.
9. The integrated molten copper slag depletion-side and top blowing reduction process of claim 1, wherein the depleting agent is FeS or FeS2One or more of pyrite, copper concentrate and carbonaceous leaner, wherein the reducing agent is one or more of coke, charcoal, bituminous coal and coking coal, and the slagging agent is CaO and CaF2One or more of lime, limestone and fluorite.
10. The integrated dilution-side-top combined converting and reducing method for molten copper slag according to claim 1, wherein the reducing agent is added according to the molar content of oxygen in the depleted slag ferrous oxide being 1.0-1.5 times, and the slag former is added according to the binary basicity of the slag being 1.0-1.4.
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| CN202110467927.6A CN113201653A (en) | 2021-04-28 | 2021-04-28 | Dilution-side-top composite converting and reducing integrated method for molten copper slag |
| PCT/CN2021/096790 WO2022227179A1 (en) | 2021-04-28 | 2021-05-28 | Molten copper slag depletion and side-top combined blowing reduction integrated method |
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| CN113817924A (en) * | 2021-09-23 | 2021-12-21 | 长沙有色冶金设计研究院有限公司 | Method for producing blister copper by smelting copper dross and smelting device thereof |
| CN114959295A (en) * | 2022-01-07 | 2022-08-30 | 昆明理工大学 | Method for reduction and dilution in copper slag furnace |
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