CN101210280A - Comprehensive utilization method for copper-containing sulfuric acid thermal baking slag - Google Patents
Comprehensive utilization method for copper-containing sulfuric acid thermal baking slag Download PDFInfo
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- CN101210280A CN101210280A CNA2006101721972A CN200610172197A CN101210280A CN 101210280 A CN101210280 A CN 101210280A CN A2006101721972 A CNA2006101721972 A CN A2006101721972A CN 200610172197 A CN200610172197 A CN 200610172197A CN 101210280 A CN101210280 A CN 101210280A
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- rotary kiln
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- sulfuric acid
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- 239000010949 copper Substances 0.000 title claims abstract description 39
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 38
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000002893 slag Substances 0.000 title claims description 37
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims description 35
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000000463 material Substances 0.000 claims abstract description 30
- 239000003818 cinder Substances 0.000 claims abstract description 25
- 229910052742 iron Inorganic materials 0.000 claims abstract description 23
- 239000012141 concentrate Substances 0.000 claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 13
- 229910052737 gold Inorganic materials 0.000 claims abstract description 11
- 229910052709 silver Inorganic materials 0.000 claims abstract description 11
- 238000005188 flotation Methods 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 23
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 16
- 239000003546 flue gas Substances 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 14
- 239000004576 sand Substances 0.000 claims description 13
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims description 5
- 239000003830 anthracite Substances 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000005660 chlorination reaction Methods 0.000 abstract description 21
- 238000006722 reduction reaction Methods 0.000 abstract description 15
- 238000012545 processing Methods 0.000 abstract description 9
- 239000000654 additive Substances 0.000 abstract description 8
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052683 pyrite Inorganic materials 0.000 abstract description 8
- 239000011028 pyrite Substances 0.000 abstract description 8
- 238000011084 recovery Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000003245 coal Substances 0.000 abstract description 2
- 238000000227 grinding Methods 0.000 abstract description 2
- 230000003009 desulfurizing effect Effects 0.000 abstract 1
- 238000012994 industrial processing Methods 0.000 abstract 1
- 239000000843 powder Substances 0.000 abstract 1
- 238000010791 quenching Methods 0.000 abstract 1
- 238000005204 segregation Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000007599 discharging Methods 0.000 description 9
- 239000010931 gold Substances 0.000 description 9
- 238000007885 magnetic separation Methods 0.000 description 9
- 230000002829 reductive effect Effects 0.000 description 9
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 8
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 7
- 229960004643 cupric oxide Drugs 0.000 description 7
- 239000005751 Copper oxide Substances 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 229910000431 copper oxide Inorganic materials 0.000 description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 239000003500 flue dust Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 230000003203 everyday effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000012716 precipitator Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229960004424 carbon dioxide Drugs 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000002817 coal dust Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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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
The invention discloses a comprehensive utilization method of copper-containing hot pyrite cinder, which comprises the following steps of: conveying hot pyrite cinder with a temperature of 900 to 950 DEG C discharged from a desulfurizing baking furnace in acid-making process into a rotary kiln, adding industrial salt and coke powder or smokeless coal powder into the kiln, respectively having an amount of 0.5 to 1.2% and 2 to 4% the weight of the pyrite cinder, keeping the baking temperature in the kiln at 780 to 820 DEG C, and baking for 60 to 90 min; and water-quenching the baked materials, ball-grinding, recovering copper concentrate containing Au and Ag by floatation, and magnetically selecting high-quality iron concentrate from the flotation tailing. The invention can carry out chlorination and reduction reaction by using the self-enthalpy of the pyrite cinder of pyrite ore and can conveniently adjust and control the weak reduction reaction atmosphere in the rear segment of the rotary kiln to achieve sufficient contact between the materials and additives, thus achieving good processing effect, high recovery rate, good economic benefit and low processing cost. The invention can be used for large-scale industrial processing.
Description
Technical field
The present invention relates to copper-containing sulfuric acid is burnt the method that slag for comprehensive utilizes, specifically handle to obtain high-grade iron ore concentrate ore deposit and recovery method of comprehensive utilization based on the precious metal of copper by chloridizing roasting.
Background technology
The sulfate cinder that produces in the sulphuric acid process (claiming sulfate slag, pyrite cinder, pyrite cinder again) is one of main solid waste of chemical industry generation.Common every production 1t sulfuric acid can discharge the pyrite cinder of 0.8～1.5t, the annual discharging about 7 * 10 in the whole nation
6T accounts for 1/3 of chemical sludge.Because China generally adopts the low-grade sulfurous iron ore relieving haperacidity that contains, therefore, ferrous grade is generally lower in the sulfate cinder, generally is about 30～50%, the highlyest is no more than 55%.Because ferrous grade is lower, it is bad to be directly used in the ironmaking economical effectiveness, and also contain Cu, Pb, Zn etc. in the sulfate cinder to smelting iron disadvantageous detrimental impurity, therefore, domestic sulfate cinder generally will be through handling to improve the iron grade and to reduce oxious component content as iron-smelting raw material.
The most frequently used treatment process is magnetizing roasting-magnetic separation process.The article that is published in the 53rd～56 page of " environmental engineering " magazine 1999 the 4th phase, " research of southization sulfate slag magnetizing roasting-magnetic separation process " by name as Hu Binsheng etc. shows: at 700 ℃ of maturing temperatures, burning slag rotary kiln stop 30 minutes, under the coal dust volume 3% roasting system, reach at 2.33～3.0 o'clock in burning slag susceptibility, ball milling 5～10 minutes, through the secondary magnetic separation, can obtain concentrate yield 65%, iron recovery 80%, the iron concentrate grade ore dressing result more than 63%.But this method can not make the copper content in the sulfate cinder reduce, and also can cause the further richness of copper in the iron ore concentrate long-pending after magnetic separation, and therefore, this method only is adapted to the processing that cupric not or cupric are lower than 0.2% sulfate cinder.
Having the researchist to study with the chlorination reduction roasting method in recent years is that segregation process removes and reclaim(ed) sulfuric acid burns copper metal in the slag.Segregation process is former to be to be used for handling refractory copper oxide ore.
Be called in the 4th phase of " non-ferrous metal " calendar year 2001 in " handling refractory copper oxide ore with novel segregation process " literary composition according to the Xiao An hero: one section segregation process is that ore is joined in the rotary kiln with Industrial Salt and fine coal, heats simultaneously and the reaction of emanating; Two sections segregation processes are handled copper oxide ore and are divided into the section of preheating and chloridizing roasting section, heating and segregation reaction are carried out in two steps, two sections segregation processes of TORCO adopt ebullated bed preheating oven and vertical Reaktionsofen, and two sections segregation processes of Mitsui adopt cyclone type preheating oven and reacting in rotary kiln stove.Though principle is identical when handling copper oxide ore with sulfate cinder with segregation process, owing to two kinds of raw material properties differ greatly, thereby the technical qualification difference of control is also bigger, and technical process and equipment are also inequality, need the researchist further to be studied.
Storing up the article that modest and prudent grade is published in " Hebei College of Science and Engineering's journal " the 25th the 4th phase of volume " comprehensive utilization of Tongling sulfate slag " by name discloses: the chlorination reducing roasting process be with sulfate slag with addition of a certain proportion of reductive agent (as coke powder) and chlorizating agent (as NaCl), in stove, apply certain temperature and carry out roasting.Under weak reducing atmosphere, Fe
2O
3Be reduced into Fe by carbon or carbon monoxide
3O
4Simultaneously, NaCl and gangue react, the output hydrogen chloride gas.Hydrogen chloride gas produces the evaporable cuprous chloride with the cupric oxide reaction again.The carbon that is added then adsorbs and is reduced into metallic copper in coke surface, separates with gangue by method for floating and reclaims copper ore concentrates; And silver has the behavior identical with copper in the ore, and gold is also reclaimed when flotation.Test can be obtained the iron ore concentrate of 63.40% grade, the rate of recovery height of iron, copper, gold and silver under optimum conditions by magnetic separation.Experimental result is satisfactory, has proved the feasibility that breaks away from the copper in the sulfate slag with segregation process.Can above-mentioned research be to obtain under laboratory condition, because the reduction of copper is strict to reaction atmosphere, is difficult to control in suitability for industrialized production, therefore find the processing method of a suitable suitability for industrialized production still perplexing the researchist.
Summary of the invention
The method of comprehensive utilization that the purpose of this invention is to provide a kind of copper-containing sulfuric acid thermal baking slag utilizes the segregation process principle to handle sulfate cinder and reclaim precious metals such as copper, gold and silver by selecting suitable process conditions, to satisfy need of industrial production.
The method of comprehensive utilization of copper-containing sulfuric acid thermal baking slag of the present invention comprises the following steps:
(1) temperature that acid-making process desulphurizing roasting fire grate is gone out is sent in the rotary kiln at 900～950 ℃ thermal baking slag, and in rotary kiln, add Industrial Salt and coke powder or pulverized anthracite, the add-on of Industrial Salt, coke powder or pulverized anthracite is respectively to send into 0.5～1.2%, 2～4% of sulfate cinder weight in the rotary kiln, keep the interior maturing temperature of kiln at 780～820 ℃, control material roasting time was at 60～90 minutes;
(2) to above-mentioned rotary kiln baking after the material of shrend carry out ball milling and reclaim to obtain to contain the fine copper sand of Au, Ag with flotation process;
(3) above-mentioned flotation tailings is obtained high-grade iron ore concentrate with magnetic method.
The chlorination reduction reaction is carried out in middle temperature (750～850 ℃), the temperature of sulfurous iron ore desulphurizing roasting is 900～950 ℃, about about 900 ℃ of the burning slag of coming out of the stove (the overflow sand and the flue dust of coming out of the stove) self heat content temperature, utilize slag roasting self heat content to carry out the chlorination reduction reaction, not only saved to burning the construction investment of the essential preheating of slag for comprehensive utilization, and saved slag roasting a large amount of energy consumptions of preheating and power, the cost that burns the slag for comprehensive utilization can be reduced significantly.Principal reaction process in the above-mentioned rotary kiln is:
(1) decomposition of NaCl:
2NaCl+H
2O+SiO
2＝Na
2SiO
3+2HCl↑
(2) chlorination of oxide compound copper and volatilization:
(3) reduction process:
C+H
2O＝CO↑+H
2↑
3Fe
2O
3+CO＝2Fe
3O
4+CO
2
6Fe
2O
3+C＝4Fe
3O
4+CO
2
Gold and silver in reaction after the transition, with copper be carrier with the copper suction on the reductive carbon granule, Fe
2O
3Be reduced into Fe
3O
4, obtaining to contain the fine copper sand of Au, Ag through grinding flotation, the flotation tailings obtains iron ore concentrate through magnetic separation, makes sulfate cinder obtain comprehensive utilization.
Because what sulfate cinder was different with copper oxide ore is that the content of copper is extremely low, its content generally is lower than 0.7%, and is therefore more strict to the control of reaction conditions, requires material can fully contact with additive, simultaneously reaction atmosphere is required also higherly, otherwise be unfavorable for the segregation of copper.And the flue gas of desulphurizing roasting stove belongs to strong oxidizing property atmosphere, and this flue gas contains high SO
2Concentration, and the flue gas of chlorination reduction reaction kiln belongs to weak reducing atmosphere, is two kinds of complete flue gas conditions inequality, the flue gas of desulphurizing roasting stove is scurried into chlorination reduction reaction kiln, not only can destroy its weak reducing atmosphere, under the condition of misoperation, and SO
2Can be reduced into single sulphur and be adsorbed on the carbon granule surface, the carrying out of overslaugh chlorination reduction reaction.In addition, the flue gas of chlorination reduction reaction kiln contains HCl, scurries into the desulphurizing roasting stove flue gas processing of desulphurizing roasting stove is made troubles, and can make valuable metal (Cu, Au, Ag) volatilization loss.Therefore, sulfuric acid thermal baking slag of the present invention is not sent in the rotary kiln by the desulphurizing roasting stove under the air-proof condition of gas blowby mutually continuously in the front and back section.
Temperature can descend to some extent when sulfate cinder entered rotary kiln, in addition, the additive Industrial Salt and the coke powder of adding also can be brought moisture content into, and heat dissipation is all wanted in the intensification of water evaporates and additive, when temperature is lower than 780 ℃, need be in rotary kiln the concurrent heating amount to keep kiln temperature at 780～820 ℃.The present invention is under the condition of not destroying chlorination reduction reaction requirement weakly reducing atmosphere, employing feeds temperature 1000～1150 ℃ of neutral burning gas mode additional heat in rotary kiln, the hot gas that is replenished is neutrality, to avoid high-temperature fuel gas to contain excessive oxygen and coke powder burning and to make temperature control.
Because solid, solid reaction between gentle, solid that chlorination reaction belongs to, bed thickness is thick more, helps making material and additive to mix more, can improve the effect of chlorination reduction reaction.Two sections segregation processes of TORCO are selected to handle copper oxide ore with vertical Reaktionsofen as chlorination reactor and also just are being based on this mechanism, and shaft furnace belongs to moving-bed, its main drawback is that material produces segregation and channel in moving-bed, it is uneven that material is contacted with additive, chlorination reduction reaction inequality, reaction effect is poor, and very low sulfate cinder chlorination is extremely disadvantageous for cupric for this.Therefore the present invention selects rotary kiln as chlorination reactor.In order to improve bed thickness, help chlorination reaction and carry out, the present invention designs the stacking factor of rotary kiln 25～30%, makes the HCl of output in the bed of material can obtain abundant recycle, and the flue gas in the control bed of material contains CO/CO
2Volume ratio between 5～7%, be beneficial to Fe
2O
3Be reduced into Fe
3O
4, the HCl volume percent content in the control bed of material flue gas is beneficial to chlorination reaction between 0.3～0.8%, and contains HCl from the flue gas that rotary kiln is discharged and be lower than 0.3%, and this also helps the processing of flue gas.When rotary kiln rotates, burn slag and mixed well with additive, solid, consolidate reaction gentle, between consolidating and more improve, more help improving copper and noble metal recovery rate.
The present invention utilizes sulfurous iron ore desulphurizing roasting slag self heat content to carry out the chlorination reduction reaction, not only saved to burning the construction investment of the essential preheating of slag for comprehensive utilization, and saved slag roasting a large amount of energy consumptions of preheating and power, the cost that burns the slag for comprehensive utilization can be reduced significantly.Adopt special feed appliance that the atmosphere of preceding backend reactors is separated preferably, make the weak reduction reaction atmosphere of regulating and control back segment become easily, be convenient to production operation; The rotary kiln that adopts high fill-factor is as chlorination reactor, and material can fully contact with additive, sufficient reacting, and treatment effect is good, and cupric is lower than 0.2% in the resulting iron ore concentrate, can satisfy the ironmaking requirement; The rate of recovery of iron, copper, gold and silver can reach 80～85%, 70～85%, 60～70%, 50～65% respectively, rate of recovery height, and better economic benefit can be used for heavy industrialization and handles.To contain HCl＜0.3% amount low for gas in the flue gas that rotary kiln is discharged, and is easy to handle qualified discharge.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Fig. 2 is the feed appliance structural representation.
Fig. 3 is the rotary structure synoptic diagram.
Embodiment
Its major ingredient of the selected sulfuric acid thermal baking slag of present embodiment: Fe48～53%, Cu0.3～0.7%, Au0.5～1.5g/t, Ag4～50g/t.
As shown in Figure 1, the flue dust of overflow sand that the desulphurizing roasting fire grate is gone out and the collection of its dust-precipitator is sent in the feed appliance after blending bin mixes.Above-mentioned mixed temperature of charge is about 780 ℃.
Certainly, in order to improve the temperature of charge that enters rotary kiln, also the overflow sand that can directly the desulphurizing roasting fire grate be gone out is sent in the feed appliance, and the flue dust that dust-precipitator is collected returns in the desulphurizing roasting stove.Like this, send into the overflow sand heat content height of rotary kiln, about about 900 ℃ of temperature can reduce or not need to the rotary kiln concurrent heating.
The feed appliance structure comprises a vertical feed cavity 8 and a horizontal discharging chamber 9 as shown in Figure 2, and vertical feed cavity bottom communicates with horizontal discharging chamber, is provided with in the horizontal discharging chamber to be used for blowing with the removable blow gun 1 to the rotary kiln convey materials to horizontal discharging chamber.On the wall of vertical feed cavity and joint, discharging chamber, be fixed with the puopulsion unit 2 that advances blowpipe by internal screw.Vertical feed cavity 7 upper ends communicate with the discharge port of blending bin 6 bottoms, the overflow sand of preheating oven flows into blending bin 6 through overflow port 3, the flue dust that dust-precipitator is collected flows into blending bin through filling tube 5, after mixing, agitator 4 enters vertical feed cavity 7, between vertical feed cavity and horizontal discharging chamber, form material nature angle of rest (repose), and reach the purpose of material packing gas, utilize in the horizontal discharging chamber movably blowpipe, send into air intercepting material nature angle of rest (repose) in a small amount, and fluidisation burning slag is sent into the reacting in rotary kiln device.
Rotary structure as shown in Figure 3.The kiln body of rotary kiln feed end 16 and discharge end 24 is tapered, and the full cone angle of feed end is 70 °～120 °, and the full cone angle beta of discharge end is 40 °～50 °, and the stacking factor of rotary kiln can reach 25～30%.Direct tube section is provided with heat exchanger 18 at feed end in the kiln, its length account for kiln direct tube section length 1/3～3/5.Between kiln hood and the material feeding box 12, be tightly connected with woven fiber glass compensating axial contact type sealing device 15 respectively between kiln tail and the nesting box 25, part 23 is the tensioning mechanism of tightness system 15 among Fig. 3.Temperature is sent into material feeding box 12 at 900～950 ℃ high temperature sulfate cinder by feed appliance 11, Industrial Salt and coke powder or pulverized anthracite add in the rotary kiln by the filling tube 13 of material feeding box 12 tops continuously, add-on accounts for 0.5～1.2% and 2～4% of the sulfate cinder weight of sending into rotary kiln respectively, kiln temperature is controlled at 780～820 ℃, and the flue gas in the control bed of material contains CO/CO
2Ratio between 2～8%, HCl content is controlled between 0.3～0.8%.Control material in rotary kiln roasting time at 60～90 minutes.Roasting sand 21 in the kiln flows into nesting box 25 shrends and discharges from water seal arrangement 26.Reaction material flows in the nesting box shrend water seal arrangement and discharges.Tail gas discharging after flue gas cooling and wet dust collector system and alkali lye absorption and alkali liquor circulating system processing.
If kiln temperature is lower than 780 ℃, can in kiln, feed through abundant burning, temperature at 1000～1150 ℃ of neutral burning gas.In order to improve the utilising efficiency of replenishing heat energy, can in kiln, emanant heat exchanger commonly used be set direct tube section, as High Temperature Gas and the intermediate carrier that burns slag exchanging heat, imitate to improve the heat of burning the slag concurrent heating.Material feeding box at rotary kiln also is provided with the electric heater that the material of sending into is heated, so that material is carried out concurrent heating.Material feeding box 12 is provided with hot gas inlet mouth 10.The high-temperature fuel gas of concurrent heating (temperature is the combustion gas of low oxygen content for about 1000～1150 ℃) is sent into rotary kiln from the material feeding box inlet mouth, makes and keeps 780～820 ℃ temperature of reaction in the kiln.Part 19,20,22 among Fig. 3 is respectively hot merit determinator, drive cone and backspin rolls.
Obtain to contain the fine copper sand of gold and silver through ball milling, classification, flotation by the shrend roasting sand of rotary kiln discharge.The flotation tailings obtains iron ore concentrate through magnetic separation.
Through the processing of above-mentioned technology, obtainable index is: fine copper sand contains Cu8～18%, contains Au20～80g/t, contains Ag50～850g/t, and the rate of recovery is respectively 70～85%, 60～70%, 50～65%.Magnetic separation can obtain the iron ore concentrate that contains Fe60～64%, and the rate 80～85% of returning of iron contains Cu＜0.2% in the iron ore concentrate, satisfy the requirement that iron is smelted.
Calculate to handle 120 tons of average compositions that contain the sulfate cinder of Fe53%, Cu0.56%, Au0.8g/t, Ag8g/t every day, but every day, output contained the fine copper sand 3.92t of Cu12%, Au15.92g/t, Ag146.94g/t.Magnetic separation can obtain to contain the iron ore concentrate 80.76t of Fe63%, Cu0.17% every day.About 51018 yuan/day of its output value, about 425 yuan of the output value of one ton of sulfate cinder of processing, the processing cost of sulfuric acid thermal baking slag per ton (the desulphurizing roasting cost counts sulfuric acid) is about 227 yuan, and its economic benefit is considerable.
Claims (5)
1. the method for comprehensive utilization of a copper-containing sulfuric acid thermal baking slag is characterized in that it comprises the steps:
(1) temperature that acid-making process desulphurizing roasting fire grate is gone out is sent in the rotary kiln at 900～950 ℃ thermal baking slag, and in rotary kiln, add Industrial Salt and coke powder or pulverized anthracite, the add-on of Industrial Salt, coke powder or pulverized anthracite is respectively to send into 0.5～1.2%, 2～4% of sulfate cinder weight in the rotary kiln, keep the interior maturing temperature of kiln at 780～820 ℃, control material roasting time was at 60～90 minutes;
(2) to above-mentioned rotary kiln baking after the material of shrend carry out ball milling and reclaim to obtain to contain the fine copper sand of Au, Ag with flotation process;
(3) above-mentioned flotation tailings is obtained high-grade iron ore concentrate with magnetic method.
2. the method for comprehensive utilization of copper-containing sulfuric acid thermal baking slag according to claim 1 is characterized in that sulfuric acid thermal baking slag do not sent in the rotary kiln by the desulphurizing roasting stove under the air-proof condition of gas blowby mutually continuously in the front and back section.
3. the method for comprehensive utilization of copper-containing sulfuric acid thermal baking slag according to claim 1 is characterized in that when rotary kiln temperature is lower than 780 ℃, in rotary kiln, feed temperature at 1000～1150 ℃ of neutral burning gas with additional heat in rotary kiln.
4. the method for comprehensive utilization of copper-containing sulfuric acid thermal baking slag according to claim 1 is characterized in that the stacking factor of rotary kiln designs 25～30%.
5. the method for comprehensive utilization of copper-containing sulfuric acid thermal baking slag according to claim 1 is characterized in that the flue gas of controlling in the rotary kiln bed of material contains CO/CO
2Volume ratio between 5～7%, contain HCl gas volume per-cent between 0.3～0.8%.
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| CN102094122A (en) * | 2010-12-01 | 2011-06-15 | 何侠 | Method for preparing sulfuric acid slag into metal iron and heat-resistant metal by roasting method |
| CN102220479A (en) * | 2011-05-05 | 2011-10-19 | 昆明晶石矿冶有限公司 | Beneficiation method for comprehensive recovery of valuable metals from sulfuric acid residues through chlorination and segregation |
| CN105268558A (en) * | 2015-08-19 | 2016-01-27 | 江西理工大学 | Method for comprehensively utilizing associated valuable components of high-sulfur and low-copper complex copper sulphide ore |
| CN106238197A (en) * | 2016-08-11 | 2016-12-21 | 李国民 | Copper concentrate produces the roasting beneficiation method of " copper matte regulus " |
| CN107326190A (en) * | 2017-05-23 | 2017-11-07 | 西北矿冶研究院 | Resource utilization method of lead-zinc-silver-containing smelting slag |
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| CN111270079A (en) * | 2020-03-19 | 2020-06-12 | 中国恩菲工程技术有限公司 | Method for recovering valuable metals in copper slag |
| CN112916196A (en) * | 2020-12-29 | 2021-06-08 | 内蒙古黄岗矿业有限责任公司 | Mineral processing technology for obtaining independent copper and zinc concentrates from low-copper high-zinc sulfide ores |
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| CN102094122A (en) * | 2010-12-01 | 2011-06-15 | 何侠 | Method for preparing sulfuric acid slag into metal iron and heat-resistant metal by roasting method |
| CN102220479A (en) * | 2011-05-05 | 2011-10-19 | 昆明晶石矿冶有限公司 | Beneficiation method for comprehensive recovery of valuable metals from sulfuric acid residues through chlorination and segregation |
| CN105268558B (en) * | 2015-08-19 | 2019-01-11 | 江西理工大学 | A kind of method of the valuable component comprehensive utilization of the low cuprate complex copper-sulphide ores association of high-sulfur |
| CN105268558A (en) * | 2015-08-19 | 2016-01-27 | 江西理工大学 | Method for comprehensively utilizing associated valuable components of high-sulfur and low-copper complex copper sulphide ore |
| CN106238197A (en) * | 2016-08-11 | 2016-12-21 | 李国民 | Copper concentrate produces the roasting beneficiation method of " copper matte regulus " |
| CN106238197B (en) * | 2016-08-11 | 2018-08-31 | 李国民 | Copper concentrate produces the roasting-beneficiation method of " copper matte regulus " |
| CN107326190A (en) * | 2017-05-23 | 2017-11-07 | 西北矿冶研究院 | Resource utilization method of lead-zinc-silver-containing smelting slag |
| CN107326190B (en) * | 2017-05-23 | 2019-09-20 | 西北矿冶研究院 | A resource utilization method of lead-containing zinc-silver smelting slag |
| CN109652657A (en) * | 2019-02-26 | 2019-04-19 | 昆明理工大学 | A kind of method of the low-grade sulfate slag comprehensive utilization of cupric, lead, zinc, sulphur |
| CN111270079A (en) * | 2020-03-19 | 2020-06-12 | 中国恩菲工程技术有限公司 | Method for recovering valuable metals in copper slag |
| CN112916196A (en) * | 2020-12-29 | 2021-06-08 | 内蒙古黄岗矿业有限责任公司 | Mineral processing technology for obtaining independent copper and zinc concentrates from low-copper high-zinc sulfide ores |
| CN112916196B (en) * | 2020-12-29 | 2022-08-23 | 内蒙古黄岗矿业有限责任公司 | Mineral processing technology for obtaining independent copper and zinc concentrates from low-copper high-zinc sulfide ores |
| WO2024000080A1 (en) * | 2022-06-27 | 2024-01-04 | Rousseau Aravena Patricio | Continuous thermochemical cycle process for producing hydrogen by pretreating copper concentrates |
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