CN102978318A - Method for realizing phosphorus removal of oolitic high-phosphorus iron ores by combining enhanced gas-based reduction and high-temperature smelting separation - Google Patents
Method for realizing phosphorus removal of oolitic high-phosphorus iron ores by combining enhanced gas-based reduction and high-temperature smelting separation Download PDFInfo
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Abstract
The invention discloses a method for realizing phosphorus removal of oolitic high-phosphorus iron ores by combining enhanced gas-based reduction and high-temperature smelting separation, which realizes direct preparation of low-phosphorus molten iron from oolitic high-phosphorus iron ores. The invention is characterized in that the method comprises the following steps: crushing materials; performing microwave pretreatment; performing fluidized bed gas-based reduction; adjusting a slag system; and performing high-temperature smelting separation. Compared with the existing method for treating oolitic high-phosphorus iron ores, the method disclosed by the invention has the following remarkable beneficial effects: ore powder does not need to be subjected to fine grinding treatment, thereby reducing the energy consumption for ore grinding; through the microwave pretreatment, the oolitic structure of the high-phosphorus iron ore powder and compact apatite layers are destroyed, and multiple tiny cracks are formed in ore powder particles; the ore powder subjected to the microwave pretreatment is deeply reduced within a relatively short time in the fluidized gas-based reduction process, and the metallization rate of the ore powder can be up to 85% or above; and after the slag system of the ore powder is subjected to fine adjustment, the reduced ore powder is subjected to high-temperature smelting separation to be directly prepared into thermal state low-phosphorus molten iron having a phosphorus content of 0.2-0.4%, and meanwhile, the metal iron recovery rate is up to 85% or above. The invention has the characteristics of high iron recovery rate and good phosphorus removal effect, and provides a new dressing and smelting technology for the utilization of oolitic high-phosphorus iron ores which are difficult to treat.
Description
Technical field:
The technique of iron is put forward in the dephosphorization that the present invention relates to oolitic high phosphorus iron ore, particularly a kind of high efficiente callback metallic iron and the directly technique of the hot low-phosphorous molten iron of preparation.Belong to ferrous metallurgy-ironmaking field.
Background technology:
A large amount of roe shape phosphorus-containing iron ores are buried in Hunan, area, Hubei Province and the Yangtze valley in China, about 7,000,000,000 tons in western Hubei Province proven reserve.This mineral primary categories is rhombohedral iron ore, rhombspar, clinochlore, quartz and phosphatic rock (fluorine or pyroclasite).Phosphorus mainly exists with phosphatic rock (hydroxyapatite or fluorapatite) form therein; Some is to be filled in the middle of the oolith for this kind phosphatic rock, is to form interbed with rhombohedral iron ore in the form of a ring but considerable part is also arranged, and forms a kind of layered structure of onion shape.How efficiently to utilize such Mineral resources to begin to obtain showing great attention to of domestic a plurality of iron and steel corporation and mining company.Domestic many R﹠D institutions and university all begun this ore deposit dephosphorization is proposed the research of iron simultaneously.At present domestic and international dephosphorization research for high-phosphorus iron ore can be divided into following five large types:
(i) biological phosphate-eliminating: most bacteriums, fungi, actinomycetes all have molten phosphorus effect.In recent years, utilize the research of Biodephosphorization very active, these microorganisms produce sour reduction system P value by metabolism and make the dissolving of phosphorus ore thing.Simultaneously metabolism acid and Ca
2+, Mg
2+, Al
3+Ion is integrated the dissolving that the complex compound that forms is further facilitated the phosphorus ore thing, and secondly the excessive phosphorus characteristic of taking the photograph of some bacterium also provides condition for using microbe carries out the high-phosphorus iron ore dephosphorization.Biological dephosphorization mainly refer to adopt thiobacillus to the high phosphorus sample ore with carrying out pre-treatment, insoluble sulfide is converted into the sulfuric acid of solubility, makes to contain to be exposed at the inner fine calcium phosphate of iron ore to be convenient in the solution and the stripping of molten phosphorus agent generation chemical reaction.Patent (CN200710034844.8) and patent (CN200910088966.4) have been comprised for what oolitic high phosphorus iron ore dephosphorization problem adopted Biological Phosphorus Removal Processes.But the main drawback of biological dephosphorization method is dephosphorization cycle long (generally needing 3-6 month time), is difficult to satisfy the needs of Iron And Steel Industry scale operation.
(ii) chemistry leaching dephosphorization: the chemical process dephosphorization adopts the inorganic acids such as sulfuric acid, hydrochloric acid or nitric acid that ore is carried out the acidleach dephosphorization, and the phosphorus ore thing in the ore is monomer dissociation fully, and leach liquor can remove the phosphorus containg substances that is dissolved out rapidly.Zhang (Hydrometallurgy, 21 (1998): 255-275) and Chen (Minerals Engineering, 12 (1999): result 1083-1092.) shows: sulfuric acid to iron ore dephosphorization effect best. secondly be nitric acid, hydrochloric acid since its to have a stronger volatility dephosphorization effect relatively relatively poor. when sulfuric acid concentration was 1%, the iron loss that leaches the stirring velocity that it is suitable that the 20min. dephosphorization rate the is 91.61%. suitable extraction time that is 624r/min. under the room temperature and be in the 20min. acidleach process was lower than 0.25%.Patent (CN200910094153.6) discloses a kind of technique of carrying out dephosphorization with the technique of the assisted and strengthened acidleach of ultrasonic wave.When patent (CN201110221510.8) adopts acidleach related measure has also been taked in the discharging of spent acid.These operational paths have certain industrial prospect.Its shortcoming is that the chemical reagent consumption is large, and cost is high, and iron loss is also larger, can't be used in industrial production.And spent acid causes the impact on environment easily, is difficult to process.
(iii) magnetization (or reduction) roasting, coal-based direct reduction+magnetic separation separates:, limonite red to high-phosphor oolitic, Ai Guanghua (mining metallurgical engineering, 29 (2009): the 45-50) flow process of employing reducing roasting+magnetic separation, can access the iron grade more than 60%, the iron ore concentrate of iron recovery more than 70%, and the content of phosphorus in the iron ore concentrate is reduced to 0.2% index preferably from about 0.65%, Li Guangtao (mining industry wall bulletin, 465 (2008): 27-3) adopt similar method to make the phosphorus content in the breeze drop to 0.3%.Patent (CN201010269488.X and CN 201110108641.5) has been announced respectively the method for two all decreasing phosphorus of high-phosphorus iron ore by adopting microwave reduction-magnetic separations.But because phosphorus ore thing disseminated grain size is too tiny in this kakoxene, must carries out fine grinding to breeze and process.This phosphorus removing method is unsatisfactory, and the comprehensive cost of this method is still high.
(iv) selectivity is reunited and added reverse flotation: reverse flotation is that one of main method of current iron ore dephosphorization is because the impure mineral disseminated grain sizes such as phosphatic rock are superfine, collecting was difficult after fine grinding made the monomer whose cleavage, the rate of recovery is low. and in conjunction with the advantage of reverse flotation dephosphorization technology, the selectivity agglomerate divides the separation of electing the microfine phosphorus ore containing as that an effective way is provided.Lin Xianghui (mining metallurgical engineering, 27 (2007): 28-29) reported iron content 42.05%, phosphorous 0.98% iron ore adopts magnetic separation one selectivity agglomerate desliming one reverse floatation process, has obtained the iron content 56.29%. rate of recovery 59.21%, phosphorous 0.10% iron ore concentrate.But for the oolitic high phosphorus iron ore of onion-like structure, the weak effect of this more traditional beneficiation method, iron loss is high.This industry equally also exists breeze must fine grinding and the long defective of technical process.
(v) pyrometallurgical smelting method dephosphorization: mainly refer to HISMELT method processing high-phosphorus iron ore and hot metal pretreatment, the converter process dephosphorization.The HISMELT smelting reduction process is processed high Rock Phosphate (72Min BPL), be to be mixed in proportion use with other high grade ores, simultaneously in the slag high FeO content as cost (iron and steel, 47 (2012): 20-26).This be the rate of recovery that reduces iron be cost.
In sum, in general, not only there is the shortcoming of technical process complexity or long processing period in these process imagines at present, and are difficult to reach energy consumption, and phosphorus content and metal recovery rate be the target of optimum simultaneously.
The inventor is devoted to the research project of the reduction of fluidization powder iron ore gas base and microwave metallurgical always.And in research process, finished the present invention.For existing problem in the present oolitic high phosphorus iron ore dephosphorization process, the inventor thinks in traditional blast furnace+converter metallurgical process, reason owing to flow process itself, some detrimental impurity elements in the iron ore, can not remove in the blast furnace ironmaking process such as P etc., phosphorus in the furnace charge all enters in the molten iron, and chief reason is owing to [C] in the molten iron is saturated.By reacting (1) so that furnace charge P all enters in the molten iron.
(P
2O
5)+5[C]＝2[P]+5CO(g)。(1)
Because when changing molten iron into take coal or coke as the iron in the iron-smelting process high-phosphorus iron ore of main reductive agent, reaction (1) can't be avoided.Caused can't dephosphorization in the reduction of phosphorus ore thing in the breeze.But at the operational path of processing the high-phosphorus iron ore dephosphorization with the reduction of gas base, can avoid reaction (1) to the disadvantageous effect of dephosphorization.Phosphorus ore containing is at CO or H
2The reaction that may exist under the atmosphere has:
Ca
3(PO
4)
2+5CO(g)＝3CaO+P
2(g)+5CO
2(g)ΔG＝934.67-0.16T (kJ)，(2)
Ca
3(PO
4)
2+8H
2(g)＝3CaO+2PH
3(g)+5H
2O(g)ΔG＝961.47-0.10T (kJ)。(3)
The equilibrium constant to reaction (2-3) calculates as can be known, and these two reaction equilibrium constants are very little, and therefore the very difficult forward of reaction carries out.Utilize reducing gas H
2, CO carries out High Temperature Gas base reduction to this ore deposit, can avoid reducing the appearance of the too much carbon residue in the rear sample ore, just can in high temperature melting minute process, can avoid reacting the appearance of (1), thereby reach the purpose that the phosphorus that makes in the ore deposit is enriched in the slag phase.The applicant finds the effectively dephosphorization and directly produce hot low-phosphorous molten iron of this technique in to gas base reduction+high temperature melting division technique route processing oolitic high phosphorus iron ore.But because the onion-like structure of oolitic high phosphorus iron ore uniqueness and the compactness of ring-type apatite layer, the gas base reducing metal rate of breeze is low.Under study for action, we find at CO or H
2Atmosphere, reduction temperature 800-1000 ℃, under the condition of recovery time 2-5h, the degree of metalization of this breeze is difficult to surpass 70%, has a strong impact on the slag iron separating effect in the molten division technique of next step slag iron.For the poor problem of oolitic high phosphorus iron ore breeze gas base reduction effect, this patent proposes to adopt microwave method for preprocessing to strengthen the gas base reduction effect of breeze.Utilize microwave that oolitic high phosphorus iron ore is carried out pre-treatment, can realize various ore deposits in the oolith are heated under different temperature rise rates and reached the purpose of the micropore structure that changes the oolitic high phosphorus iron ore particle.Thereby improve the gas base reducing property of this breeze, the gas base reduction of breeze is strengthened.For the problem of slag iron inferior separating effect, the present invention added a small amount of carbonate additive at molten minute in the process, utilized that the decomposition of carbonate produces product (CO under the high temperature
2) a molten minute system is played stirring action, the solid product that carbonate decomposition stays can become dephosphorizing agent and the dissolving agent in the slag system, thereby to improve the dephosphorizing capacity of slag in the molten minute system.Utilize these means to realize the thorough separation of slag iron, improve to greatest extent metal recovery rate and the purpose that reaches the dephosphorization of low-carbon (LC) molten iron.
Summary of the invention:
The objective of the invention is in order to realize that high efficiency dephosphorating and high-level efficiency reclaim metallic iron.It mainly is a kind of method of processing greater than 50% difficult oolitic high phosphorus iron ore for the iron grade.The present invention intends adopting Microwave Pretreatment breeze+fluidized-bed gas base reduction+high temperature melting shunt lead, by this breeze of Microwave Pretreatment, changes the microscopic pores structure of this breeze, impels the reducing property of this breeze to improve.By in reduzate, adding small part additive (carbonate), adjust slag system with the fusing point that reduces molten minute process slag system with prevent slag to the rephosphorization of iron, and the CO that further utilizes the decomposition of carbonate to produce
2Realization is to the stirring of molten minute system, to reach quick, the fully separation of slag iron.
Concrete technology step of the present invention is as follows:
A kind of gas base reduction associating high temperature melting of strengthening divides the method that realizes the oolitic high phosphorus iron ore dephosphorization, specifically may further comprise the steps:
(1). material crushing: getting difficult oolitic high phosphorus iron ore is raw material, with crusher it is broken into fine-grannular, the breeze after the fragmentation 300 ℃ lower dry more than 3 hours until finish-drying;
(2). Microwave Pretreatment: a certain amount of breeze is put into microwave oven; The target temperature of breeze is made as 800 ℃.Regulating microwave power makes the breeze temperature rise rate reach 150-200 ℃/min; The breeze temperature reaches target temperature, behind the constant temperature 1-3min, begins cooling; After the breeze temperature drops to room temperature, obtain the breeze after the Microwave Pretreatment;
(3) fluid bed reduction: the breeze after the Microwave Pretreatment adds in the fluidized-bed reactor, utilizes reducing gas to carry out fluidized reduction 60-90min, and fluidizing gas velocity is 0.20m/s, and reduction temperature is 1000 ℃ in the fluidized-bed;
(4). the slag system adjustment: form according to the gangue of breeze, in the good breeze of reduction with addition of powder additive, the abundant mixing of the breeze after the reduction and additive;
(5). high temperature melting divides: behind above-mentioned mixed breeze charge piezometric piece, realize after molten minute that in High Temperature Furnaces Heating Apparatus slag iron separates; Directly prepare hot low-phosphorous molten iron and high phosphorus slag; Realize the oolitic high phosphorus iron ore dephosphorization.In the described step (1), be raw material with oolitic high phosphorus iron ore, with crusher it be crushed to granularity less than 1mm.
In the described step (1), oolitic high phosphorus iron ore is phosphorous massfraction 0.8-1.2%, the difficult refractory iron ore of all iron content more than 50%.
Further, in the described step (1), the breeze after the fragmentation is lower dry 3-5 hour at 300 ℃; Until after drying under this temperature, sample is no longer weightless.
In the described step (2), in the bed of material, directly insert K type thermopair, be used for temperature survey and monitoring; The temperature of breeze material is recorded by this thermopair in the microwave reactor, and microwave heating is by open close type SCR control, and thermocouple measuring temperature shows and the silicon controlled working state control is finished by digital instrument.
Further, in the described step (2), the target temperature of breeze is made as 800 ℃.Start microwave heating, the target temperature of breeze is made as 800 ℃; Set microwave power so that breeze material temperature rise rate reaches 150-200 ℃/min intensification; The breeze temperature reaches target temperature and stops microwave heating, begins cooling behind the insulation 1-3min; After breeze naturally cools to room temperature, obtain the breeze after the Microwave Pretreatment.
Reducing gas is CO, H described in the described step (3)
2Or CO and H
2The percent by volume sum surpasses 90% metallurgy reducing gas.Obtain degree of metalization greater than 85% breeze.
Powder additive is CaCO described in the described step (4)
3And Na
2CO
3CaCO
3Add-on is for reaching in the molten minute process slag system basicity close to 1.0, Na
2CO
3Add-on for reduction after the 0-5% of powdered ore quality.
The condition that high temperature melting divides in the described step (5) is molten minute temperature 1550-1600 ℃, and molten minute time 5-10min realizes that slag iron separates; Directly obtain hot low-phosphorous molten iron and high phosphorus slag.The phosphorus content of hot low-phosphorous molten iron is less than 0.4mass%, and the metallic iron rate of recovery is greater than 85%.The phosphorus content of metallic iron has satisfied converter steelmaking to the requirement of molten iron, can directly enter converter or Electric furnace steel making operation, and rich phosphorus slag can prepare phosphate fertilizer after further processing.
The invention has the beneficial effects as follows:
(1). breeze needn't fine grinding.The granularity of breeze only requires less than 1mm after broken, can reduce the energy consumption that ore grinding brings.
(2). microwave heating equipment only is used for the pre-treatment of breeze.The low power microwave heating installation short period of time (5-8min) of adopting is carried out radiation heating to breeze, utilize microwave that the characteristics that different minerals has the selectivity heating are destroyed oolith shape structure fine and close in the breeze, and at the inner Arc-shaped Cracks that forms numerous micro-cracks and develop along apatite layer of mineral powder granular, so that the gas base reduction process of next step of breeze is strengthened.
(3). utilize fluid bed reduction speed fast, the sufficient advantage of gas-solid contact in the reactor, simultaneously because the breeze granularity is larger, breeze is difficult for producing the phenomenon of bonding defluidization in reduction process, can within a short period of time the rhombohedral iron ore of breeze be reduced to metallic iron.
(4). form by adjusting slag system, the decomposition of additive carbonate is played stirring action realization dephosphorization of molten iron and is separated with slag iron melting a minute system under the dephosphorizing capacity that utilizes gangue mineral and a small amount of slag system that additive forms in the ore and the hot conditions.Thereby divide in the process at high temperature melting, the phosphorus overwhelming majority of phosphatic rock is retained in the slag, and slag iron is thoroughly separated.Obtain the steel-making processing that hot low-phosphorous molten iron directly carries out next step.
Description of drawings
Fig. 1 is that the present invention realizes that the dephosphorization of oolitic high phosphorus iron ore carries the process flow sheet of iron;
Fig. 2 a is SEM Electronic Speculum figure and the regional area enlarged view behind the oolitic high phosphorus iron ore breeze fluid bed reduction of example 1 of the present invention;
Fig. 2 b is the regional area EDS analytical results behind the oolitic high phosphorus iron ore breeze fluid bed reduction of example 1 of the present invention.
Embodiment:
Below in conjunction with specific embodiment technical scheme of the present invention is described further.
Table 1 is the chemical ingredients of used oolitic high phosphorus iron ore powder among all embodiment.
Table 1 high-phosphorus iron ore meal component (mass%)
Embodiment 1:
Fig. 1 is that the present invention realizes that the dephosphorization of oolitic high phosphorus iron ore carries the process flow sheet of iron; As shown in Figure 1, a kind of gas base reduction associating high temperature melting of strengthening divides the method that realizes the oolitic high phosphorus iron ore dephosphorization, comprises the steps:
(1). material crushing: this oolitic high phosphorus iron ore is crushed to granularity less than 1mm, and the gained breeze is lower dry 3 hours at 300 ℃.
(2). Microwave Pretreatment: take by weighing the 1000g breeze and place microwave heating equipment; Insert K type thermopair in the breeze bed of material, the voltage of thermocouple measurement gained directly is shown as the breeze temperature by digital instrument; The reactor microwave input power is by open close type SCR control, and simultaneously digital instrument control silicon controlled is open close.Set the reactor microwave power, so that the temperature rise rate of breeze reaches 150-200 ℃/min, the breeze top temperature is set as 800 ℃; Constant temperature 3min after the intensification of the breeze bed of material reaches design temperature stops microwave heating.
(3). fluid bed reduction: the breeze after the Microwave Pretreatment adds fluidized-bed reactor and carries out fluidized reduction; Fluidizing gas velocity is 0.20m/s, and reduction temperature is 1000 ℃ in the fluidized-bed, reducing gas upgrading coke-oven gas (20%CO, 70%H
210%N
2) as reducing gas, recovery time 60min; The breeze degree of metalization reaches 90.1%.From Fig. 2 a and Fig. 2 b, can find out that mineral powder granular is fully reduced.
(4). the slag system adjustment: breeze is with addition of analytical pure CaCO after the reduction
3Powder, its add-on be after the used reduction powdered ore quality 8.0%, breeze and CaCO after the reduction
3The abundant mixing of powder.
(5). high temperature melting divides: be positioned in the high purity aluminium oxide crucible after a molten minute sample that mixes is pressed into agglomerate in batches, the overcoat plumbago crucible again; At room temperature plumbago crucible is put into High Temperature Furnaces Heating Apparatus; 10 ℃/min of time variable control temperature rise rate, furnace temperature to 1600 ℃ beginning constant temperature; Insulation 10min realizes that slag iron separates; Directly obtain hot low-phosphorous molten iron and high phosphorus slag.Subsequently, furnace temperature is cooled to 500 ℃ with 10 ℃/min, takes out sample after naturally cooling to room temperature again.Gas is protected in all the time logical argon gas (500ml/min) conduct in the experimentation.Gold Samples belongs to phosphorous 0.32mass% in the iron sample, metal recovery rate 86% after the cooling
Embodiment 2:
(1). material crushing: oolitic high phosphorus iron ore is crushed to granularity less than 1mm, and the gained breeze is lower dry 5 hours at 300 ℃.
(2). Microwave Pretreatment: take by weighing the 1000g breeze and place microwave heating equipment, in the breeze bed of material, insert K type thermopair.The voltage of thermocouple measurement gained directly is shown as the breeze temperature by digital instrument; The reactor microwave input power is by open close type SCR control, and simultaneously digital instrument control silicon controlled is open close.Set the reactor microwave power, so that the breeze temperature rise rate reaches 150-200 ℃/min; The breeze top temperature is set as 800 ℃, and constant temperature 3min after the intensification of the breeze bed of material reaches design temperature stops microwave heating, naturally cools to room temperature.
(3). fluid bed reduction: the breeze after the Microwave Pretreatment adds fluidized-bed reactor and carries out fluidized reduction; Fluidizing gas velocity is 0.20m/s, and reduction temperature is 1000 ℃ in the fluidized-bed, with the COREX output coal gas as reducing gas (68%CO, 22%H
2, 10%N
2), recovery time 90min; The breeze degree of metalization reaches 89.5%.
(4). the slag system adjustment: breeze is with addition of a certain proportion of additive and evenly mixing after the reduction, and additive is analytical pure CaCO
3Powder and analytical pure Na
2CO
3Powder; CaCO
3Add-on be after the used reduction powdered ore quality 6.0%, other Na
2CO
3Add-on be sample ore after the used reduction quality 3.0%; Breeze and the abundant mixing of all additives.
(5). high temperature melting divides: the molten minute sample of mixing is pressed in batches agglomerate and is placed in the high purity aluminium oxide crucible, again the overcoat plumbago crucible; Under the room temperature plumbago crucible is entered in the High Temperature Furnaces Heating Apparatus; 10 ℃/min of time variable control temperature rise rate begins constant temperature after the furnace temperature to 1550 ℃, and insulation 5min realizes that slag iron separates; Directly obtain hot low-phosphorous molten iron and high phosphorus slag.Subsequently, furnace temperature is cooled to 500 ℃ with 10 ℃/min, takes out sample after naturally cooling to room temperature again.Gas is protected in all the time logical argon gas (500ml/min) conduct in the experimentation.Gold Samples belongs to phosphorous 0.25mass% in the iron sample, metal recovery rate 86% after the cooling
Embodiment 3:
(1). material crushing: oolitic high phosphorus iron ore tentatively is crushed to granularity less than 1mm, and the gained breeze is lower dry 4 hours at 300 ℃.
(2). Microwave Pretreatment: take by weighing the 1000g breeze and place microwave heating equipment; Insert K type thermopair in the bed of material, the voltage of thermocouple measurement gained directly is shown as the breeze temperature by digital instrument, and the reactor microwave input power is by open close type SCR control, and digital instrument control silicon controlled is open close.Set the reactor microwave power, so that the temperature rise rate of breeze reaches 150-200 ℃/min, the breeze top temperature is set as 800 ℃, and constant temperature 3min after the intensification of the breeze bed of material reaches design temperature stops microwave heating.
(3). fluid bed reduction: breeze after the Microwave Pretreatment adds fluidized-bed reactor and carries out fluidized reduction, and fluidizing gas velocity is 0.20m/s, and reduction temperature is 1000 ℃ in the fluidized-bed, with the chemical industry synthetic gas as reducing gas (45%CO, 45%H
2, 10%N
2), recovery time 60min.The breeze degree of metalization reaches 88.0%.
(4). the slag system adjustment: breeze is with addition of a certain proportion of additive and evenly mixing after the reduction; Additive is analytical pure CaCO
3Powder and analytical pure Na
2CO
3Powder, CaCO
3Add-on be sample ore after the used reduction quality 5%, other Na
2CO
3Add-on be sample ore after the used reduction quality 5%; The abundant mixing of breeze and additive.
(5). high temperature melting divides: the molten minute sample of mixing is pressed in batches agglomerate and is placed in the high purity aluminium oxide crucible, again the overcoat plumbago crucible; Then plumbago crucible is put into High Temperature Furnaces Heating Apparatus, 10 ℃/min of time variable control temperature rise rate, furnace temperature to 1550 ℃ beginning constant temperature, insulation 5min realizes that slag iron separates; Directly obtain hot low-phosphorous molten iron and high phosphorus slag.Subsequently, furnace temperature is cooled to 500 ℃ with 10 ℃/min, takes out sample after naturally cooling to room temperature again.Gas is protected in all the time logical argon gas (500ml/min) conduct in the experimentation.Gold Samples belongs to phosphorous 0.22mass% in the iron sample, metal recovery rate 85% after the cooling.
Claims (8)
1. strengthen the method that gas base reduction associating high temperature melting divides realization oolitic high phosphorus iron ore dephosphorization for one kind, it is characterized in that, specifically may further comprise the steps:
(1) material crushing: getting difficult oolitic high phosphorus iron ore is raw material, with crusher it is broken into fine-grannular, the breeze after the fragmentation 300 ℃ lower dry more than 3 hours until finish-drying;
(2) Microwave Pretreatment: a certain amount of breeze is put into microwave oven; The target temperature of breeze is made as 800 ℃; Regulating microwave power makes the breeze temperature rise rate reach 150-200 ℃/min; The breeze temperature reaches target temperature, behind the constant temperature 1-3min, begins cooling; After the breeze temperature drops to room temperature, obtain the breeze after the Microwave Pretreatment;
(3) fluid bed reduction: the breeze after the Microwave Pretreatment adds in the fluidized-bed reactor, utilizes reducing gas to carry out fluidized reduction 60-90 min, and fluidizing gas velocity is 0.20 m/s, and reduction temperature is 1000 ℃ in the fluidized-bed;
(4) slag system adjustment: form according to the gangue of breeze, in the good breeze of reduction with addition of powder additive, the abundant mixing of the breeze after the reduction and additive;
(5) high temperature melting divides: behind above-mentioned mixed breeze charge piezometric piece, realize after molten minute that in High Temperature Furnaces Heating Apparatus slag iron separates; Directly prepare hot low-phosphorous molten iron and high phosphorus slag; Realize the oolitic high phosphorus iron ore dephosphorization.
2. the method for described oolitic high phosphorus iron ore dephosphorus iron extraction according to claim 1 is characterized in that, in the described step (1), is raw material with oolitic high phosphorus iron ore, with crusher it is crushed to granularity less than 1mm.
3. the method for described oolitic high phosphorus iron ore dephosphorus iron extraction according to claim 1 is characterized in that in the described step (1), oolitic high phosphorus iron ore is phosphorous massfraction 0.8-1.2%, the difficult refractory iron ore of all iron content more than 50%.
4. the method for described oolitic high phosphorus iron ore dephosphorus iron extraction according to claim 1 is characterized in that, in the described step (1), the breeze after the fragmentation is lower dry 3-5 hours at 300 ℃; Until after drying under this temperature, sample is no longer weightless.
5. the method for described oolitic high phosphorus iron ore dephosphorus iron extraction according to claim 1 is characterized in that, in the described step (2), directly inserts K type thermopair in the bed of material, is used for temperature survey and monitoring; The temperature of breeze material is recorded by this thermopair in the microwave reactor, and microwave heating is by open close type SCR control, and thermocouple measuring temperature shows and the silicon controlled working state control is finished by digital instrument.
6. the method for described oolitic high phosphorus iron ore dephosphorus iron extraction according to claim 1, it is characterized in that: reducing gas is CO, H described in the described step (3)
2Or CO and H
2The percent by volume sum surpasses the metallurgy reducing gas of 90 %.
7. the method for described oolitic high phosphorus iron ore dephosphorus iron extraction according to claim 1, it is characterized in that: powder additive is CaCO described in the described step (4)
3And Na
2CO
3In at least a; CaCO
3Add-on is for reaching in the molten minute process slag system basicity close to 1.0, Na
2CO
3Add-on for reduction after the 0-5% of powdered ore quality.
8. the method for described oolitic high phosphorus iron ore dephosphorus iron extraction according to claim 1, it is characterized in that: the condition that high temperature melting divides in the described step (5) is molten minute temperature 1550-1600 ℃, molten minute time 5-10 min realizes the separation of slag iron; Directly obtain hot low-phosphorous molten iron and high phosphorus slag.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| KR101630986B1 (en) | 2014-12-19 | 2016-06-16 | 주식회사 포스코 | Method of manufacturing low phosphor reduced iron using high phosphor iron ore |
| CN106544461A (en) * | 2016-11-01 | 2017-03-29 | 武汉科技大学 | Based on the method that the high-phosphor oolitic hematite of Efco-Northrup furnace prepares conversion pig |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103290158A (en) * | 2013-05-29 | 2013-09-11 | 北京科技大学 | Method for realizing dephosphorization of olitic high-phosphorus iron ore by use of biomass charcoal |
| CN104726629A (en) * | 2013-12-20 | 2015-06-24 | Posco公司 | Method and apparatus for manufacturing molten iron |
| KR101630986B1 (en) | 2014-12-19 | 2016-06-16 | 주식회사 포스코 | Method of manufacturing low phosphor reduced iron using high phosphor iron ore |
| CN106544461A (en) * | 2016-11-01 | 2017-03-29 | 武汉科技大学 | Based on the method that the high-phosphor oolitic hematite of Efco-Northrup furnace prepares conversion pig |
| JP2020020010A (en) * | 2018-08-02 | 2020-02-06 | 日本製鉄株式会社 | Reduction method of high-phosphorus iron ore |
| JP7099149B2 (en) | 2018-08-02 | 2022-07-12 | 日本製鉄株式会社 | Reduction method of high-phosphorus iron ore |
| CN108842056A (en) * | 2018-09-07 | 2018-11-20 | 安徽工业大学 | A kind of oolitic hematite quickly heats the method that reduction prepares reduced iron powder |
| CN114525373A (en) * | 2022-01-20 | 2022-05-24 | 华北理工大学 | Method for desulfurizing and dephosphorizing iron ore powder through microwave hydrogen reduction |
| CN114525373B (en) * | 2022-01-20 | 2023-12-08 | 华北理工大学 | Method for desulfurizing and phosphorus by reducing iron ore powder with microwave hydrogen |
| CN115404339A (en) * | 2022-07-28 | 2022-11-29 | 北京氢冶科技有限公司 | Method for developing and utilizing oolitic high-phosphorus iron ore |
| CN115404339B (en) * | 2022-07-28 | 2024-04-09 | 北京氢冶科技有限公司 | Method for developing and utilizing oolitic high-phosphorus iron ore |
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