CN104745800A - Three-stage suspension roasting-magnetic separation method for hematite-limonite mixed iron ores - Google Patents
Three-stage suspension roasting-magnetic separation method for hematite-limonite mixed iron ores Download PDFInfo
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Abstract
The invention relates to a three-stage suspension roasting-magnetic separation method for hematite-limonite mixed iron ores and belongs to the technical field of mineral processing. The method comprises the following steps: (1) milling the hematite-limonite mixed iron ores, then, putting the milled material into a suspension reacting furnace, and enabling the material to be in a suspended state; heating to the temperature of 450-800 DEG C, so as to carry out preoxidation roasting; (2) stopping heating, and introducing nitrogen gas to displace air; introducing reductive gas, and enabling the material to be in a suspended loose state, so as to carry out reduction; (3) displacing unreacted residual reductive gas, introducing air to carry out reoxidation when the temperature is lowered to 250-400 DEG C, and then, taking out and carrying out secondary milling; (4) carrying out magnetic separation under the condition that the intensity of a magnetic field is 60-100kA/m. According to the method disclosed by the invention, the process is simple, the recovery ratio of highly-difficultly-separated ores is increased, the adaptability of the method is strong, the process is safe and reliable, and the product quality is uniform and stable; the method has the advantages of energy saving and consumption reducing.
Description
Technical field
The invention belongs to technical field of mineral processing, particularly the russet compound iron ore of one three sections of suspension roasting-magnetic selection methods.
Background technology
China's Iron And Steel Industry fast development, iron ore demand sharply rises; China's iron ore grade is low, natural endowment is poor, selecting and purchasing cost is high, causes domestic iron ore to produce the demand that can not meet development of iron & steel industry far away; 2014, China's imported Fe ore 9.33 hundred million tons, external dependence degree was up to 78.5%, and iron ore external dependence degree is too high, and the international discourse of China Steel and security are reduced further.Within 2014, imported Fe ore price is reduced to 70 dollars/below t by the 130 dollars/t at the beginning of the year, and domestic iron ore is corresponding price reduction more than 40% also, causes domestic iron mine to be close to whole industry loss; Iron And Steel Industry is pillar industry in national economy, to the social people's livelihood of guarantee, there is irreplaceable effect, China Supply of iron ore deficiency has become " bottleneck " of restriction national economic development, even becomes a great realistic problem with industrialization, urbanization and modernization whole process; Therefore, the Efficient Development strengthening China's Refractory iron ore resource utilizes has important strategic importance.
Rhombohedral iron ore-limonite mixed ore is typical Refractory iron ore resource, and its chemical composition is not fixed, and disseminated grain size is thin, and easy argillization in comminution process, belong to Refractory iron ore stone; Current China proven reserve is about 12.3 hundred million t, is mainly distributed in the provinces such as Yunnan, Guangdong, Guangxi, Shandong, Guizhou, Jiangxi, Xinjiang and Fujian; Owing to being subject to the restriction that limonite ore character (very easily argillization), high intensity magnetic separation equipment (p-20 μm of iron mineral rate of recovery are poor), System of Flotation Reagent and magnetizing roasting cost are high, limonite resource utilization is extremely low, major part does not have effective recycling, or does not exploit at all; Iron wherein in rhombohedral iron ore accounts for 30 ~ 90%, iron in limonite accounts for 5 ~ 60%; Because its mineral disseminated grain size is thin, ore structures is complicated, and it is larger that it sorts difficulty.Single Beneficiation flowsheet (gravity treatment, magnetic separation and flotation etc.), magnetic-floating combined process flow is had at present, reducing roasting-magnetic separation-leaching flow process and chloridizing roasting flow process etc. to the typical ore-dressing technique of hematite-limonite.
Magnetizing roasting-magnetic separation refers to carries out complicated physics chemical action by material or ore heating in corresponding atmosphere, makes weak magnetism mineral change ferromagnetism iron mineral (Fe into
3o
4), the magnetic contrast between recycling mineral carries out magnetic separation; Common magnetizing roasting mode has shaft roasting, rotary kiln baking, fluosolids roasting etc.; Qiu Chongdong etc. adopt flash magnetization roasting-weak magnetic separation process and chloridizing roasting-weak magnetic separation process to carry out simultaneous test to elder brother's steel steamed bun restaurant hematite-limonite; Test-results shows, flash magnetization roasting-weak magnetic separation process effectively can improve iron concentrate grade, obtains the good index of iron ore concentrate productive rate 55.27%, grade 59.47%, the rate of recovery 92.86%; Chlorination segregation-weak magnetic separation process can obtain iron ore concentrate productive rate 36.26%, Iron grade 77.24%(containing P0.22%), the index of iron recovery 80.20%, but the recycling of chlorizating agent needs to be studied further in this technique, and process costs is higher, also need the gordian technique researching and solving many through engineering approaches.
During above magnetizing roasting technical finesse rhombohedral iron ore-limonite composite ore, there is the problem of following three aspects: 1, because iron mineral character is inconsistent, under identical reductive condition, the reaction of different minerals is asynchronous, reducing material complete reaction can not generate the Fe of magnetic
3o
4, or occurred that reduction generated non-magnetic FeO, and then cause separation index poor; 2, heating material and reduction synchronously carry out, and reducing atmosphere is difficult to ensure, industrializing implementation difficulty; 3,0 ~ 25mm fine particle stage material cannot be processed.
Summary of the invention
The object of the invention is to provide a kind of russet compound iron ore three sections of suspension roasting-magnetic selection methods, by by rhombohedral iron ore-limonite mixed ore preoxidation-reduce-reoxidize suspension roasting, obtains the iron ore concentrate that sorting index is higher.
Method of the present invention is carried out according to the following steps:
1, preoxidation: russet compound iron ore ore grinding is accounted for 40 ~ 80% of gross weight to granularity-0.074mm, then puts into suspension reaction stove, pass into air in suspension reaction stove, makes material be suspended state; Preoxidized roast is carried out in heating material to 450 ~ 800 in suspension reaction stove DEG C, and be now oxidizing atmosphere in suspension reaction stove, the time of preoxidation is 10 ~ 120s; Described russet compound iron ore is rhombohedral iron ore-limonite mixed ore;
2, accumulation of heat reduction: be incubated rear stopping heating, passed into nitrogen replacement and go out air in suspension reaction stove; Then in suspension reaction stove, pass into reducing gas, make material be in suspension loose condition (of surface), the heat utilizing material self to save reduces, and the recovery time is 5 ~ 60 seconds;
3, reoxidize: reduction terminates rear stopping and passing into reducing gas, in suspension reaction stove, pass into nitrogen replacement go out unreacted residual reducing gas, by the water coolant of suspension reaction stove chuck, suspension reaction stove is lowered the temperature, when temperature is down to 250 ~ 400 DEG C, in suspension reaction stove, pass into air reoxidize, when the material in suspension reaction stove is cooled to below 100 DEG C, material is taken out and carries out secondary grinding;
4, magnetic separation: when the material after secondary grinding accounts for 40 ~ 80% of gross weight to the part of granularity-0.044mm, the material after secondary grinding is carried out magnetic separation under magneticstrength 60 ~ 100kA/m condition, obtain magnetic concentrate and magnetic tailing.
In aforesaid method, be in suspension roaster, pass into liquefied gas and light to heat by heating material in suspension roaster.
In aforesaid method, preoxidation, reduce and reoxidize in process, in the chuck of suspension roaster, circulation has water coolant all the time.
In aforesaid method, continue to pass into nitrogen in step 2 while passing into reducing gas, the throughput ratio of reducing gas and nitrogen is 1:(1 ~ 10).
Above-mentioned reducing gas selects carbon monoxide.
In aforesaid method, the reaction formula of the preoxidation in step 1 is:
Fe
2O
3·2H
2O(s) = Fe
2O
3(s)+ 2H
2O(g) (1)
Limonite (Fe
2o
32H
2o) Fe is converted into
2o
3.
In aforesaid method, the reaction formula of the reduction in step 2 is:
3Fe
2O
3(s)+CO(g)=2Fe
3O
4(s)+CO
2(g) (2)
Fe in material
2o
3be reduced to Fe
3o
4.
In aforesaid method, in the material after reoxidizing in step 3, main component is Armco magnetic iron γ-Fe
2o
3and Fe
3o
4; Wherein γ-Fe
2o
3weight content at 50 ~ 90%, Fe
3o
4weight content 5 ~ 45%.
In aforesaid method, a large amount of reaction heat is released in the reaction that reoxidizes in step 3, carries out heat exchange with the water coolant of suspension reaction stove chuck, is converted into water vapour and reclaims.
In aforesaid method, the rate of recovery of iron is 80 ~ 95%.
The Iron grade of the magnetic concentrate that aforesaid method obtains is 64 ~ 66%.
Compared with prior art, feature of the present invention and beneficial effect are:
(1) for the rhombohedral iron ore-limonite mixed ore of current China large amount of complex difficulty choosing, the iron mineral uniform conversion of wherein composition inequality is made to be the γ-Fe that magnetic is stronger by the preoxidation-three phases that reduces-reoxidize
2o
3, the exploitation for this kind of iron ore utilizes and provides a kind of well sorting method; Process take Reaktionsofen as major equipment, by the control of different oxidations, reducing atmosphere and temperature, makes it that corresponding physicochemical change occur, achieves the phase transformation of iron mineral, finally obtain the product γ-Fe of uniform quality
2o
3, and realize being recycled of waste heat in the process; The high efficiente callback achieving this Refractory iron ore stone eventually through ore grinding-magnetic separation utilizes;
(2) the method realizes effective sorting of a large amount of unserviceable limonite, rhombohedral iron ore composite ore so far on the one hand, vitalizes a large amount of iron ore deposit; Significantly can improve on the other hand the rate of recovery of refractory ore, the more conventional sorting process rate of recovery improves more than 15 percentage points, reaches energy-conservation, consumption reduction, synergy object.
(3) propose rhombohedral iron ore-limonite mixed ore pre-oxidation technology: compared with other magnetizing roasting technology, ensure that all iron minerals in material all change Fe into by the preoxidation stage
2o
3, ensure that the reduction homogeneity of final product, so stronger to the ore adaptability of process;
(4) mover iron ore accumulation of heat autoreduction technology: only at preoxidation process, ore is heated, when ore enters reduction furnace chamber, the heat utilizing ore self to lay in and reducing gas complete reaction, make heating and Reduced separating, avoid the possibility of reducing gas blast, safe and reliable, for industrialization equipment provides technology prototype;
(5) the continuous suspended state control techniques of heterogeneous body ore particles in stoving oven is proposed.In whole roasting process, material particles particle under the effect of gas is suspended in gas phase more, is in good dispersion state, and gas-solid can be made fully to contact, and make reaction heat transfer, mass transfer effect better, roasting process speed of response is fast, and uniform in quality is stablized;
(6) magnetizing roasting product Fe is proposed
3o
4reoxidizing synchronous recovery waste heat technology: by arranging cooling environment, controlling Fe in product of roasting
3o
4to γ-Fe
2o
3transform again, reclaim the heat discharged in this thing inversion of phases process.
Accompanying drawing explanation
Fig. 1 is in the method for the embodiment of the present invention 1, and phase flow schematic diagram is reduced-reoxidizes in preoxidation-accumulation of heat; In figure, A is the preoxidized roast stage, and B is for passing into nitrogen replacement air event, and C is for passing into the reducing gas stage, and D is for passing into the nitrogen replacement reducing gas stage, and E is temperature-fall period, and F is for reoxidizing the stage;
Fig. 2 is the russet compound iron ore three sections of suspension roastings-magnetic selection method schematic flow sheet of the embodiment of the present invention 1.
Embodiment
The suspension roaster adopted in the embodiment of the present invention is intermittent type suspension roaster, comprise the cooling water jecket of body of heater and sidewall thereof, bottom of furnace body is provided with nitrogen inlet, gas inlet and reducing gas entrance, being provided with gas-permeable nets (air distribution plate) below furnace interior for placing response material makes the gas uniform of circulation distribute, body of heater top is provided with waste gas outlet, below body of heater, sidepiece is provided with liquefied gas burner, and liquefied gas burner is positioned at above gas-permeable nets.
Φ 180mm × 200mm tube ball mill ore grinding is adopted in the embodiment of the present invention.
Adopt Φ 50mm magnetic separation tube to carry out magnetic separation in the embodiment of the present invention to sort.
The Iron grade 30 ~ 39% of the rhombohedral iron ore adopted in the embodiment of the present invention-limonite mixed ore, by weight percentage containing FeO 1 ~ 5%, SiO
215 ~ 50%.
Material Mossbauer spectrometer after reoxidizing in the embodiment of the present invention detects, and the main component recording material is maghemite γ-Fe
2o
3with magnetite Fe
3o
4; Wherein γ-Fe
2o
3weight content 50 ~ 90%, magnetite Fe
3o
4weight content 5 ~ 45%; All the other are rhombohedral iron ore Fe
2o
3; The Mossbauer spectrometer model adopted is WSSL-10.
In the embodiment of the present invention, the air intake of step 1 is 0.8 ~ 2m/s by the flow velocity of air in suspension roaster.
In the embodiment of the present invention, in step 2, the flow proportional of reducing gas and nitrogen is 0.8 ~ 2m/s by the flow velocity of two kinds of gases in suspension roaster.
Air intake in the embodiment of the present invention in step 3 is 0.8 ~ 2m/s by the flow velocity of air in suspension roaster.
In suspension roaster, pass into liquefied gas and light to heat by heating material in suspension roaster in the embodiment of the present invention.
Embodiment 1
The main component (unit wt%) as shown in table 1 of the russet compound iron ore (rhombohedral iron ore-limonite mixed ore) adopted;
Table 1
Component | TFe | FeO | SiO 2 | Al 2O 3 | CaO |
Content | 35.25 | 1.03 | 49.41 | 0.15 | 0.39 |
Component | MgO | P | S | K | Na |
Content | 0.37 | 0.88 | 0.05 | 0.04 | 0.03 |
Chemical phase analysis result is as shown in table 2;
Table 2
Method is carried out according to the following steps:
1, preoxidation: russet compound iron ore ore grinding is accounted for 40% of gross weight to granularity-0.074mm, then puts into suspension reaction stove, pass into air in suspension reaction stove, makes material be suspended state; Heating material to 800 in suspension reaction stove DEG C is carried out preoxidized roast, and be now oxidizing atmosphere in suspension reaction stove, the time of preoxidation is 10s; Described russet compound iron ore is rhombohedral iron ore-limonite mixed ore;
2, accumulation of heat reduction: be incubated rear stopping heating, passed into nitrogen replacement and go out air in suspension reaction stove; Then in suspension reaction stove, pass into CO, make material be in suspension loose condition (of surface), the heat utilizing material self to save reduces, and the recovery time is 5 seconds; Continue while passing into CO to pass into nitrogen, the volume flow ratio of CO and nitrogen is 1:10;
3, reoxidize: reduction terminates rear stopping and passing into CO, in suspension reaction stove, pass into nitrogen replacement go out unreacted remaining CO, by the water coolant of suspension reaction stove chuck, suspension reaction stove is lowered the temperature, when temperature is down to 400 DEG C, in suspension reaction stove, pass into air reoxidize, when the material in suspension reaction stove is cooled to below 100 DEG C, material is taken out and carries out secondary grinding; In material after reoxidizing, main component is Armco magnetic iron γ-Fe
2o
3and Fe
3o
4; Wherein γ-Fe
2o
3weight content at 90%, Fe
3o
4weight content 5%; Reoxidize reaction and release a large amount of reaction heat, carry out heat exchange with the water coolant of suspension reaction stove chuck, be converted into water vapour and reclaim;
4, magnetic separation: when the material after secondary grinding accounts for 40% of gross weight to the part of granularity-0.044mm, the material after secondary grinding is carried out magnetic separation under magneticstrength 60kA/m condition, obtain magnetic concentrate and magnetic tailing;
Preoxidation, reduce and reoxidize in process, in the chuck of suspension roaster, circulation has water coolant all the time;
The rate of recovery of iron is 95%; The Iron grade of magnetic concentrate is 66%.
Embodiment 2
Russet compound iron ore Iron grade 39%, by weight percentage containing FeO 3%, SiO
215%;
Method is with embodiment 1, and difference is:
(1) ore grinding accounts for 50% of gross weight to granularity-0.074mm, is heated to 700 DEG C and carries out preoxidized roast, and the time of preoxidation is 30s;
(2) recovery time is 10 seconds; The volume flow ratio of CO and nitrogen is 1:5;
(3), when temperature is down to 350 DEG C, in suspension reaction stove, passes into air reoxidize; In material after reoxidizing, main component is Armco magnetic iron γ-Fe
2o
3and Fe
3o
4; Wherein γ-Fe
2o
3weight content at 80%, Fe
3o
4weight content 12%;
(4), when the material after secondary grinding to the part of granularity-0.044mm accounts for 50% of gross weight, the material after secondary grinding is carried out magnetic separation under magneticstrength 70kA/m condition; The rate of recovery of iron is 90%; The Iron grade of magnetic concentrate is 65%.
Embodiment 3
Russet compound iron ore Iron grade 33%, by weight percentage containing FeO4%, SiO
220%;
Method is with embodiment 1, and difference is:
(1) ore grinding accounts for 60% of gross weight to granularity-0.074mm, is heated to 600 DEG C and carries out preoxidized roast, and the time of preoxidation is 60s;
(2) recovery time is 30 seconds; The volume flow ratio of CO and nitrogen is 1:3;
(3), when temperature is down to 300 DEG C, in suspension reaction stove, passes into air reoxidize; In material after reoxidizing, main component is Armco magnetic iron γ-Fe
2o
3and Fe
3o
4; Wherein γ-Fe
2o
3weight content at 60%, Fe
3o
4weight content 31%;
(4), when the material after secondary grinding to the part of granularity-0.044mm accounts for 60% of gross weight, the material after secondary grinding is carried out magnetic separation under magneticstrength 80kA/m condition; The rate of recovery of iron is 85%; The Iron grade of magnetic concentrate is 65%.
Embodiment 4
Russet compound iron ore Iron grade 30%, by weight percentage containing FeO5%, SiO
233%;
Method is with embodiment 1, and difference is:
(1) ore grinding accounts for 80% of gross weight to granularity-0.074mm, is heated to 450 DEG C and carries out preoxidized roast, and the time of preoxidation is 120s;
(2) recovery time is 60 seconds; The volume flow ratio of CO and nitrogen is 1:1;
(3), when temperature is down to 250 DEG C, in suspension reaction stove, passes into air reoxidize; In material after reoxidizing, main component is Armco magnetic iron γ-Fe
2o
3and Fe
3o
4; Wherein γ-Fe
2o
3weight content at 50%, Fe
3o
4weight content 45%;
(4), when the material after secondary grinding to the part of granularity-0.044mm accounts for 80% of gross weight, the material after secondary grinding is carried out magnetic separation under magneticstrength 100kA/m condition; The rate of recovery of iron is 80%; The Iron grade of magnetic concentrate is 64%.
Claims (6)
1. russet compound iron ore three sections of suspension roasting-magnetic selection methods, is characterized in that carrying out according to the following steps:
(1) preoxidation: russet compound iron ore ore grinding is accounted for 40 ~ 80% of gross weight to granularity-0.074mm, then puts into suspension reaction stove, pass into air in suspension reaction stove, makes material be suspended state; Preoxidized roast is carried out in heating material to 450 ~ 800 in suspension reaction stove DEG C, and be now oxidizing atmosphere in suspension reaction stove, the time of preoxidation is 10 ~ 120s; Described russet compound iron ore is rhombohedral iron ore-limonite mixed ore;
(2) accumulation of heat reduction: be incubated rear stopping heating, passed into nitrogen replacement and go out air in suspension reaction stove; Then in suspension reaction stove, pass into reducing gas, make material be in suspension loose condition (of surface), the heat utilizing material self to save reduces, and the recovery time is 5 ~ 60 seconds;
(3) reoxidize: reduction terminates rear stopping and passing into reducing gas, in suspension reaction stove, pass into nitrogen replacement go out unreacted residual reducing gas, by the water coolant of suspension reaction stove chuck, suspension reaction stove is lowered the temperature, when temperature is down to 250 ~ 400 DEG C, in suspension reaction stove, pass into air reoxidize, when the material in suspension reaction stove is cooled to below 100 DEG C, material is taken out and carries out secondary grinding;
(4) magnetic separation: when the material after secondary grinding accounts for 40 ~ 80% of gross weight to the part of granularity-0.044mm, the material after secondary grinding is carried out magnetic separation under magneticstrength 60 ~ 100kA/m condition, obtain magnetic concentrate and magnetic tailing.
2. the russet compound iron ore of one according to claim 1 three sections of suspension roasting-magnetic selection methods, continue to pass into nitrogen while it is characterized in that passing into reducing gas in step (2), and the throughput ratio of reducing gas and nitrogen is 1:(1 ~ 10).
3. the russet compound iron ore of one according to claim 1 three sections of suspension roasting-magnetic selection methods, is characterized in that described reducing gas selects carbon monoxide.
4. the russet compound iron ore of one according to claim 1 three sections of suspension roasting-magnetic selection methods, is characterized in that in the material after reoxidizing in step (3), main component is Armco magnetic iron γ-Fe
2o
3and Fe
3o
4; Wherein γ-Fe
2o
3weight content at 50 ~ 90%, Fe
3o
4weight content 5 ~ 45%.
5. the russet compound iron ore of one according to claim 1 three sections of suspension roasting-magnetic selection methods, is characterized in that the rate of recovery of iron is 80 ~ 95%.
6. the russet compound iron ore of one according to claim 1 three sections of suspension roasting-magnetic selection methods, is characterized in that the Iron grade of described magnetic concentrate is 64 ~ 66%.
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