CN1348999A - Copper-nickel slag treating method - Google Patents
Copper-nickel slag treating method Download PDFInfo
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- CN1348999A CN1348999A CN00123066A CN00123066A CN1348999A CN 1348999 A CN1348999 A CN 1348999A CN 00123066 A CN00123066 A CN 00123066A CN 00123066 A CN00123066 A CN 00123066A CN 1348999 A CN1348999 A CN 1348999A
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- 239000002893 slag Substances 0.000 title claims abstract description 200
- 238000000034 method Methods 0.000 title claims abstract description 50
- 229910000570 Cupronickel Inorganic materials 0.000 title claims abstract description 17
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 title claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000005406 washing Methods 0.000 claims abstract description 43
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 40
- 230000008569 process Effects 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 57
- 229910052759 nickel Inorganic materials 0.000 claims description 31
- 239000010949 copper Substances 0.000 claims description 23
- 238000003723 Smelting Methods 0.000 claims description 22
- 239000010970 precious metal Substances 0.000 claims description 22
- 229910052802 copper Inorganic materials 0.000 claims description 20
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 claims description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 19
- 230000002829 reductive effect Effects 0.000 claims description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 239000000571 coke Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 7
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000012141 concentrate Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229910052683 pyrite Inorganic materials 0.000 claims description 6
- 239000011028 pyrite Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000003245 coal Substances 0.000 claims description 4
- 230000004907 flux Effects 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 239000010426 asphalt Substances 0.000 claims 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims 1
- 239000000292 calcium oxide Substances 0.000 claims 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims 1
- 239000007770 graphite material Substances 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 229910000510 noble metal Inorganic materials 0.000 abstract description 9
- 239000007789 gas Substances 0.000 abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 238000007667 floating Methods 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 3
- 230000005484 gravity Effects 0.000 abstract description 3
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 abstract 1
- 230000008021 deposition Effects 0.000 abstract 1
- 238000005187 foaming Methods 0.000 abstract 1
- 230000000630 rising effect Effects 0.000 abstract 1
- 229910017052 cobalt Inorganic materials 0.000 description 27
- 239000010941 cobalt Substances 0.000 description 27
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 27
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000011084 recovery Methods 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- 239000011449 brick Substances 0.000 description 6
- 238000010790 dilution Methods 0.000 description 6
- 239000012895 dilution Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000009853 pyrometallurgy Methods 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000004073 vulcanization Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 230000033764 rhythmic process Effects 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- -1 cobalt and nickel Chemical class 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical compound [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 description 1
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 description 1
- IWPMRMIANLLTTJ-UHFFFAOYSA-N cobalt(2+);sulfane Chemical compound S.[Co+2] IWPMRMIANLLTTJ-UHFFFAOYSA-N 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical group [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000009851 ferrous metallurgy Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
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- 230000008018 melting Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- YFLLTMUVNFGTIW-UHFFFAOYSA-N nickel;sulfanylidenecopper Chemical compound [Ni].[Cu]=S YFLLTMUVNFGTIW-UHFFFAOYSA-N 0.000 description 1
- 238000009856 non-ferrous metallurgy Methods 0.000 description 1
- 239000006253 pitch coke Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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- 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
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- Manufacture And Refinement Of Metals (AREA)
Abstract
A treatment method for copper-nickel thermometallurgy furnace slag is to place the reducing carbon in the bottom of slag washing furnace, inject a layer of 5-50 cm low deg. matte and 10-60 cm to-be-washed furnace slag on the carbon respectively, and produce a large amount of CO gas bubbles by means of chemical reaction between oxygen in the thermla matte and the reducing carbon, gas bubbles in the process of floating upward tring about the upper thermal matte foaming and rising to enter the upper slag layer for thermal matte slag washing, and noble metal in the slag is recovered by matte-slag reaction. The thermal matte floated-up-into slag under the action of gravity automatically returns tack again to the furnace bottom such that slag is repeatedly washed in circulation for 30-60 min, then the slag is stood still in a thermo-insulated intermediate ladle to deposit for 30-60 min so to make sufficient deposition, and the depleted slag is discarded.
Description
The invention relates to a pyrometallurgical technique of copper and nickel, and particularly provides a hot matte slag washing method for improving the recovery rate of residual precious metals such as cobalt, nickel and copper in high-temperature furnace slag and further improving the comprehensive economic index of the pyrometallurgical technique of copper and nickel.
The refining industry of copper and nickel metal is one of the most important industrial sectors in the modern nonferrous metallurgy industry, copper, nickel and cobalt byproducts thereof are widely applied to various important industrial sectors and are indispensable raw materials in the modern machine manufacturing industry, the aviation industry, instruments and meters, transportation energy sources and national defense industry, and the metals, particularly cobalt and nickel, become one of the critical strategic materials of the modern industry due to the regionality of mineral resource distribution and the irreplaceability in the industry.
For copper sulphide ores, nickel sulphide ores or copper-nickel sulphide paragenic ores, the main task of the modern pyrometallurgical process is to oxidize the paragenetic base metal iron from the sulphides into slag and separate it from the matte, while the precious metals Cu, Ni and associated Co remain in the matte (nickel matte, matte or cobalt matte, etc.) for further hydrometallurgical refining. The main processes of pyrometallurgy are divided into two major categories, namely, smelting by burning and smelting by a flash furnace, wherein the process flow of roasting smelting is as follows: raw concentrate powder → roasting (oxidizing and desulfurizing part of iron sulfide to form iron oxide) → electric furnace smelting (or reverberatory furnace smelting to melt sulfide and oxide and realize matte/slag separation) → converter blowing (furtheroxidizing residual iron sulfide in low-grade copper matte or nickel matte to slag and separating from matte) → high matte or high nickel matte → hydrometallurgy (further refining sulfide to pure metal); the difference between the flash smelting process flow and the above process is that the roasting and smelting steps are combined into flash smelting (concentrate powder, oxygen-enriched air or pure oxygen, fuel such as coal powder or heavy oil and the like are directly injected into the furnace, the concentrate powder is melted by utilizing the high temperature generated by the combustion heat of iron sulfide, liquid drops are formed and fall into a lower sedimentation tank, and the slag/matte separation is realized under the action of a gravitational field). The further smelting and the roasting smelting process have the same flow. Because the combustion heat generated by the reaction of the iron sulfide and the oxygen is fully utilized in the smelting of the flash furnace, a large amount of energy can be saved, and the smelting cost is reduced, so that the flash furnace becomes the most competitive process flow at present.
Unlike ferrous metallurgy, copper-nickel pyrometallurgy is characterized by a large amount of waste slag, and therefore, even if the waste slag contains only a small amount of precious metals (mainly cobalt, nickel, and copper), a large economic loss is caused. How to reduce the content of residual precious metals in slag is one of the major technical problems faced by modern copper-nickel pyrometallurgy, the residual cobalt in slag is the most important loss in nickel metallurgical slag at the current price level, the economic value of the residual cobalt accounts for more than 70% of the total loss of three metals, namely cobalt, nickel and copper, and the existing research shows that the loss of cobalt in converter slag with strong oxidizing atmosphere is the largest, and most of cobalt in matte can enter into slag phase. The cobalt content in the converter slag is up to 0.5-1.4% (Xujiazhen, Ye-Guei, Wei-Guzhong, Happy, nonferrous metal, 5/1988, P31, which accounts for more than 70% of the total cobalt in the furnace matte, while the residual cobalt content in the slag of electric furnaces or flash furnaces with larger waste slag amount is up to 0.07-0.15%, so the improvement of the comprehensive technical and economic index of copper-nickel pyrometallurgy is the most key to improve the recovery rate of cobalt.
The existing research shows that the loss mechanism of noble metal such as cobalt in the slag can be divided into two types, one is that cobalt oxide forms symbiotic oxide (CoFe) with iron oxide or silicon oxide in the slag2O4Or 2CoOSi2O2) The loss of other precious metals such as nickel and copper is mainly based on the physical mechanism, while the loss of cobalt is mainly based on the chemical mechanism. The loss of the noble metal cobalt is the greatest in the more oxidizing converter slag, so that a good reductive thermodynamic condition and sufficient physical precipitation should be provided to increase the recovery of the noble metal from the slag.
In the existing copper-nickel smelting technology, electric furnace slag, reflective furnace slag and flash furnace slag have no further recovery processing technology, and direct water quenching of slag is adopted, converter slag containing more precious metals has two basic processing technologies, one is to return the converter slag to an electric furnace again, add part of coke to reduce and vulcanize cobalt and nickel chemically dissolved in the slag, and simultaneously provide enough temperature and settling time to enable sulfonium drops mechanically drawn in the slag to settle into nickel matte at the bottom. The slag depletion process (C. Draz, et al, CIMBulletin, Vol87, No981, 1994, P62) is carried out with the advantage of relatively simple operation, without the addition of new equipment and personnel, and therefore at a lower cost, but its disadvantages are also evident. (1) An effective cobalt enrichment process cannot be established, cobalt enters the electric furnace low-degree matte from the converter slag, the electric furnace low-degree matte is sent into the converter for converting, and the electric furnace low-degree matte enters the converter slag again, so that the cycle is repeated, and the yield of the cobalt is very low; (2) after the large amount of converter slag is reinjected into the electric furnace again, the slag amount of the electric furnace is increased, so that the load of the electric furnace is increased, and simultaneously, the components of the electric furnace slag are changed, and the latter can influence the obtaining of the optimal process conditions for electric furnace smelting. The other process flow for recovering the precious metals in the converter slag is to adopt a special dilution furnace to treat the converter slag, inject the high-temperature converter slag into the dilution furnace, add a proper amount of reducing agent (coke, etc.), vulcanizing agent (pyrite, etc.) and flux (quartz sand, lime, etc.), heat in the dilution furnace, reduce and vulcanize the precious metals contained in the slag into sulfonium drops, after standing and precipitating for a sufficient time, discharge the depleted slag, abandon the new converter slag, after a sulfonium layer at the bottom of the dilution furnace is accumulated to a certain depth, discharge the slag from a sulfonium discharge port, and thus, the processes are circulated repeatedly (crude and heavy, non-ferrous metals, 3/1995, P10). The process has the advantages that the converter slag can be independently treated to obtain cobalt nickel matte or cobalt copper matte, other smelting process flows are not interfered, different converter slags can be adjusted according to specific compositions of the converter slags, the treatment processes such as adding different quantities of furnace materials (coke, vulcanizing agent, quartz sand, lime and the like), selecting different treatment temperatures, heat preservation time and the like to obtain better metallurgical physical and chemical conditions, and improving the yield of precious metals in the slags, the process has the main defects that the fluidity of the slag in a dilution furnace is poor, the contact chance of precious metal oxides and carbon in the slags is small, and the slag is subjected to solid/liquid reaction, so that the reduction and vulcanization reaction speed in the furnace is slow, the treatment period is longer (generally, a better result can be obtained in 4-6 hours), the blowing production rhythm of the converter is fast (generally, the slag is placed once per hour, the production rhythms of the two are different, and the whole smelting production line is, therefore, how to intensify the reduction-vulcanization reaction in the lean electric furnace and shorten the treatment time of the converter slag is one of the important problems to be solved by the process, on the other hand, no matter the smelting furnace is returned to the furnace or the lean furnace is treated separately, the coke fragments as the main reducing agent are added from the slag surface of the converter slag, because the specific gravity of the coke is smaller than that of the slag, the reduced carbon originally floats on the slag surface, or even if the carbon is sprayed into the slag by a spray gun, the reduced carbon quickly floats from the slag to the slag surface, and under the high temperature condition, most of the carbon particles are actually oxidized and combusted as fuel. Only a small part of carbon is used as an effective reducing agent to participate in the reduction reaction of the precious metals in the slag, so the reduction efficiency is low, and the residual cobalt and nickel in the slag are difficult to be fully reduced, so the yield is relatively low.
The invention aims to provide a method for treating copper-nickel pyrometallurgical slag, which has the advantages of high reduction and vulcanization speed, strong slag treatment capacity, high recovery rate of precious metals cobalt and nickel in slag and relatively low slag treatment cost.
The invention provides a method for treating copper-nickel pyrometallurgical slag, which is characterized by comprising the following process flows of:
(1) filling a reduced carbon layer with the thickness of 5-40cm at the bottom of the slag washing furnace;
(2) injecting a layer of molten low-degree matte into the slag washing furnace to completely cover the carbon layer at the bottom of the furnace, wherein the thickness of the matte layer is 5-50cm, and the iron content in the low-degree matte is 35-60% by weight;
(3) injecting high-temperature furnace slag to be washed on the liquid level of the low-degree matte, wherein the thickness of a slag layer is 10-60cm, and meanwhile, adding a fusing agent according to the conventional method;
(4) heating the slag washing furnace, washing slag at 1200-1450 ℃, and carrying out hot matte slag washing by utilizing the self-boiling phenomenon caused by furnace bottom carbon/matte reaction, wherein the slag washing time is 10-40 minutes;
(5) and injecting the washed slag into an intermediate heat-preserving bag, standing for 20-60min to ensure that sulfonium drops involved in the slag are fully precipitated to the furnace bottom, realizing slag/sulfonium separation, and finally discarding the depleted slag to obtain bottom sulfonium for further recovering precious metals Co, Ni and Cu in the bottom sulfonium.
The quality of the bottom matte is gradually improved in the continuous operation process of the invention, and the iron content of the bottom matte can be controlled within the range of 35-60% by discharging a part of the bottom matte and adding a part of pyrite or raw concentrate.
In the carbon/sulfonium/slag system, a carbon/sulfonium interface generates high-temperature chemical reaction to generate a large amount of reducing gas CO and zero-valent iron, a sulfonium layer positioned at the bottom foams and overflows in the floating process of CO bubbles, the sulfonium layer contacts and reacts with upper slag, and finally hot sulfonium returns to the furnace bottom under the action of gravity to complete a slag washing cycle.
The reduced carbon in the process of the invention can be metallurgical coke, graphite, pitch coke or industrial coal, the shape can be regular brick shape, irregular block shape or powder particle, the paving form can be that the carbon brick form is built at the bottom of the slag washing furnace, or the paving form can be that the carbon brick form is mixed with a proper amount of adhesive, and then the mixture is paved at the bottom of the furnace and is fully tamped to form a whole. The carbon layer of the furnace bottom should be paved firmly, otherwise, the carbon layer is likely to be loosened and floated in the slag washing process.
The low-degree matte in the process of the invention can be smelting matte (electric furnace matte, flash furnace matte or reverberatory furnace matte) of a previous process, or pyrite or raw concentrate obtained by melting, or a mixture of the two, only if the Fe content is ensured to be in a specified range, the reduction of the matte is poor, the cobalt content in the waste slag is increased, and the iron content is too high, the grade of the obtained nickel matte or matte is too low, which brings unnecessary difficulty for further treatment.
The high-temperatureslag in the process of the invention refers to converter slag or electric furnace slag, reflector slag and the like in copper and nickel pyrometallurgy, and the invention has the best effect of treating the converter slag especially because the common converter slag is rich in a large amount of cobalt and nickel.
The thickness of the matte layer and the slag layer is controlled within the range, the matte layer is too thin and is not enough for slag washing, and the gas bubbles floating at the bottom are not enough to lift the matte layer and overflow to the slag layer to complete the forced slag washing process if the matte layer is too thick. Similarly, if the slag layer is too thin, the slag amount is too small, and if the slag layer is too thick, the slag washing effect is not good.
The heating method of the slag washing furnace can adopt the existing industrial heating technology, such as fuel injection (coal powder, heavy oil and the like), heat preservation agent covering the top, resistance heating or direct electrifying heating by inserting electrode bars into slag and the like, and the heating temperature is required to keep the slag in a molten state and has proper viscosity so as to obtain the best slag washing effect.
The technical principle of the invention is that the following metallurgical thermodynamic reaction is utilized to recover the noble metal chemically dissolved in an oxidation state in the slag: (1) the carbon/sulfonium reduction reaction is carried out on the carbon/sulfonium interface of the furnace bottom
The parenthesized term in the formula represents the existence state of the substance dissolved in the sulfonium. The same applies below. (2) The reaction products CO and (Fe) of the carbon/matte interface reaction continue to undergo the following slag/matte reaction to reduce the oxides in the slag to zero-valent metal:
Reaction product (Fe) produced in reactions (15) to (17)3O4) And (FeO) in turn provides the reaction materials for equations (1) - (2) continuously, i.e., completing the transfer of oxygen from the slag through the matte to the matte/carbon interface to ensure that reactions (1) - (2) continue, which in turn provides sufficient reductant and motive force for slag washing movement.
From the equations (3), (5) and (7), it can be seen that the zero-valent iron in the pyromatte is a key reducing agent for the precious metal oxides in the slag, and the higher the activity of the zero-valent iron in the matte, the stronger the reducing power of the pyromatte. One of the technical characteristics of the invention is that a large amount of zero-valent iron is generated by means of the reaction result of furnace bottom carbon/matte, and the zero-valent iron provides good thermodynamic conditions for recovering the precious metals in the slag to the maximum extent in the slag washing furnace.
The invention has obvious technical advantages that the slag washing phenomenon of self-boiling of the matte layer caused by the reducing gas CO is firstly strengthened by the thermodynamic condition and the kinetic process in the slag washing process, so that the vulcanization reduction process of the precious metal oxide in the slag is greatly accelerated, the slag washing time is shortened, and the production rhythm is accelerated. Meanwhile, the strong gas stirring also enables the reduction and vulcanization reaction in the slag to be more uniform, and the slag washing to be more thorough. Therefore, the problems that the slag treatment time is long and the technological processes are difficult to connect in the original dilution furnace technology are solved. And secondly, the reduced carbon is positioned at the bottom of the slag washing furnace and is completely covered by the bottom matte, so that the direct oxidation and combustion of the carbon in the air are avoided, and the reduction efficiency of the carbon is greatly improved. The consumption of high-quality reduced carbon is reduced, the slag surface high-temperature phenomenon caused by the combustion of carbon on the slag surface is avoided, and a process of adding the reduced carbon one by one is omitted. Thirdly, as mentioned above, the invention uses matte/slag reaction to wash slag, and the matte keeps a high activity of zero-valent iron, and the dynamic condition and thermodynamic condition of the liquid/liquid reaction are better than those of carbon/slag reaction in the original depletion furnace process, so that the invention can obtain better slag washing effect, therefore, the invention can also process the electric slag, flash slag or reflector slag (the slag has low content of precious metal and is difficult to process) which can not be processed by the original depletion furnace process. The invention is illustrated by the following examples:
FIG. 1 is a structural schematic diagram of a slag washing furnace.
Example 1
A small slag washing furnacewith the inner diameter phi of 500cm and the capacity height of 120cm is selected, a furnace lining and a furnace bottom are built by industrial refractory magnesia-chrome bricks, in order to fix a furnace bottom carbon layer, a furnace wall 15cm away from the furnace bottom is built into an inverted cone with the lower part being large and the upper part being small, the taper is about 20 degrees, see attached figure 1, and the furnace lining is dried after being built. Then a layer of graphite brick is built at the bottom of the furnace, the thickness of the graphite brick is 10cm, a groove and a tenon are respectively processed in the middle of the side surface, and the grooves and the tenons are firmly embedded with each other to prevent the graphite block from floating upwards when slag is washed. And finally, filling the gap between the furnace wall and the graphite layer with refractory mortar, tamping firmly, and baking and drying. When the device is used for the first time, a cooling furnace is preheated to about 1000 ℃ by a flame spray gun, then a layer of low-degree matte (Fe38.6 percent and S26.5 percent) with the thickness of 10cm is injected into the furnace bottom, the temperature of the matte is 1250 ℃, and then a layer of high-temperature converter nickel slag with the thickness of about 40cm is injected immediately. The content of noble metal in the slag is 0.90 percent of Co, 4.10 percent of Ni and 0.45 percent of Cu, the temperature of the slag is 1350 ℃, and 3 percent of pyrite and a proper amount of flux material are added simultaneously. After the addition was complete, the furnace lid was closed and fuel was injected into the furnace to maintain the furnace temperature at 1350 ℃. Keeping the self-boiling slag washing movement in the furnace for 15 minutes to reduce and vulcanize noble metal oxides contained in the slag, finally injecting the washed slag into a middle heat-insulating bag for standing and precipitating for 40 minutes, finally discharging cleaned depleted slag on theupper part of the middle bag, performing water quenching and discarding, and collecting cobalt and sulfur precipitated at the bottom. After the treatment of the slag washing furnace, the residual amounts of the precious metals in the waste slag are 0.03 percent of Co, 0.25 percent of Ni and 0.1 percent of Cu, and the yield rates of the precious metals are 96.7 percent of Co, 93.9 percent of Ni and 77.8 percent of Cu respectively.
Example 2.
The slag washing furnace is the same as the example 1, but the furnace bottom carbon is changed into metallurgical coke, the coke granularity is about 3-6mm, after being uniformly mixed with proper amount of fire clay, the coke is paved on the furnace bottom of the slag washing furnace, then the carbon layer is fully tamped and firm by a vibration tamping method, the carbon layer is 15cm thick, dried and preheated, then the pre-melted pyrite (FeS, containing Fe60.0 percent) is injected with the temperature of 1210 ℃ and the thickness of 40cm, and then the electric furnace slag is injected with the temperature of 20cm and the slag temperature of 1300 ℃. The contents of the noble metals in the slag are 0.15% of Co, 0.46% of Ni, 0.42% of Cu and a proper amount of flux materials, after the materials are added, the operation is the same as that of the embodiment 1, the process parameters are 1300 ℃, the slag is washed by self-boiling for 25 minutes, finally, the washed slag is injected into a middle heat-preserving bag for precipitation for 60 minutes, the cleaned depleted slag is discharged and quenched by water to be discarded, so as to obtain cobalt sulfonium precipitated at the bottom, and after the slag is treated by the slag washing furnace, the contents of the noble metals in the waste slag are 0.01% of Co, 0.10% of Ni and 0.08% of Cu, and the yield is 93.3% of Co, 72.1% of Ni and 80.9% of Cu respectively.
Comparative example 1:
in order to compare the effects of the invention, a slag washing furnace which is the same as the slag washing furnace in the embodiment 1 is selected, but a reduced carbon layer is not laid on the furnace bottom, the added charging materials during slag washing are 40cm thick slag layer of converter slag (0.90% Co, 4.1% Ni and 0.45% Cu), the slag temperature is 1360 ℃, 15% of pyrite fragments, 4% of reduced coke and a proper amount of fusing agent, the furnace temperature during slag washing is maintained at 1350 ℃ for 3 hours, other operation methods and process parameters are the same as the embodiment 1, finally, the upper layer of depleted slag is discharged and discarded after water quenching, the content of precious metals in the discarded slag is 0.25% Co, 0.9% Ni and 44.4% Cu, compared with the effects of the invention, the invention can shorten the slag washing time by 2 hours, the recovery rate of the precious metals is 24.5% cobalt, the recovery rate of nickel is 15.9% and the recovery rate of copper is 22.8% higher.
Claims (6)
1. A method for processing copper-nickel pyrometallurgical slag is characterized by comprising the following process flows:
(1) filling a reduced carbon layer with the thickness of 10-40cm at the bottom of the slag washing furnace;
(2) injecting a layer of molten low-degree matte into the slag washing furnace to completely cover the carbon layer at the bottom of the furnace, wherein the thickness of the matte layer is 5-50cm, and the iron content in the low-degree matte is 35-60% by weight;
(3) injecting high-temperature furnace slag to be washed on the liquid level of the low-degree matte, wherein the thickness of a slag layer is 10-60cm, and simultaneously adding a fusing agent;
(4) heating the slag washing furnace, washing slag at 1200-1450 ℃, and carrying out hot matte slag washing by utilizing the self-boiling phenomenon caused by furnace bottom carbon/matte reaction, wherein the slag washing time is 10-40 minutes;
(5) and injecting the washed slag into an intermediate heat-preserving bag, standing for 20-60min to ensure that sulfonium drops involved in the slag are fully precipitated to the furnace bottom, realizing slag/sulfonium separation, and finally discarding the depleted slag to obtain bottom sulfonium for further recovering precious metals Co, Ni and Cu in the bottom sulfonium.
2. The method for treating the copper-nickel pyrometallurgical slag according to claim 1, characterized in that: the reduced carbon is one or more of metallurgical coke, graphite material, asphalt coke or industrial coal.
3. The method for treating the copper-nickel pyrometallurgical slag according to claim 1, characterized in that: the low-degree matte means primary smelting matte comprising one or more of electric furnace matte, flash furnace matte or reverberatory furnace matte, copper-nickel raw concentrate or pyrite.
4. The method for treating the copper-nickel pyrometallurgical slag according to claim 1, characterized in that: the flux is silicon dioxide or calcium oxide.
5. The method for treating the copper-nickel pyrometallurgical slag according to claim 1, characterized in that: the slag is slag in copper smelting, slag in nickel smelting or slag in copper-nickel paragenic ore smelting.
6. The method for treating the copper-nickel pyrometallurgical slag according to claim 5, characterized in that: the slag is converter slag, flash slag or electric furnace slag.
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| CNB001230662A CN1181212C (en) | 2000-10-12 | 2000-10-12 | Copper-nickel slag treating method |
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| CN100587086C (en) * | 2007-09-06 | 2010-02-03 | 昆明理工大学 | Method for modifying non-ferrous metal copper slag/nickel slag by using combustible matter and preparing high-grade fuel |
| CN101838742A (en) * | 2010-05-10 | 2010-09-22 | 王平 | Method for depleting copper and nickel smelting slag |
| CN101880775A (en) * | 2010-06-10 | 2010-11-10 | 王平 | Method for diluting copper and nickel concentrate smelting slag |
| CN101545054B (en) * | 2009-02-09 | 2011-07-06 | 牛庆君 | Method for recovering nickel, copper and cobalt from a nickel, copper and cobalt smelting waste slag |
| CN101638726B (en) * | 2009-07-07 | 2012-08-29 | 中冶葫芦岛有色金属集团有限公司 | Method for harmlessly treating precipitation slag of acid production wastewater by using Ausmelt copper smelting furnace |
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| CN103834810A (en) * | 2014-03-11 | 2014-06-04 | 斯莱登（北京）化工科技有限公司 | Method for producing copper-cobalt-nickel bulk concentrate by use of copper-nickel slag |
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| CN108728664A (en) * | 2018-04-27 | 2018-11-02 | 中南大学 | A kind of method that spent ferric oxide desulfurizer strengthens copper smelting slag dilution |
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| CN113046550A (en) * | 2021-03-11 | 2021-06-29 | 金川集团股份有限公司 | Sulfuration reducing agent for reducing valuable metals in depleted electric furnace slag and preparation method thereof |
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| CN100587086C (en) * | 2007-09-06 | 2010-02-03 | 昆明理工大学 | Method for modifying non-ferrous metal copper slag/nickel slag by using combustible matter and preparing high-grade fuel |
| CN101545054B (en) * | 2009-02-09 | 2011-07-06 | 牛庆君 | Method for recovering nickel, copper and cobalt from a nickel, copper and cobalt smelting waste slag |
| CN101638726B (en) * | 2009-07-07 | 2012-08-29 | 中冶葫芦岛有色金属集团有限公司 | Method for harmlessly treating precipitation slag of acid production wastewater by using Ausmelt copper smelting furnace |
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| CN101838742B (en) * | 2010-05-10 | 2011-12-28 | 王平 | Method for depleting copper and nickel smelting slag |
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