CN112251601A - Method for recovering iron by strengthening red mud reduction of manganese-containing minerals - Google Patents
Method for recovering iron by strengthening red mud reduction of manganese-containing minerals Download PDFInfo
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- CN112251601A CN112251601A CN202011014490.2A CN202011014490A CN112251601A CN 112251601 A CN112251601 A CN 112251601A CN 202011014490 A CN202011014490 A CN 202011014490A CN 112251601 A CN112251601 A CN 112251601A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/242—Binding; Briquetting ; Granulating with binders
- C22B1/244—Binding; Briquetting ; Granulating with binders organic
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/16—Sintering; Agglomerating
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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
Abstract
The invention belongs to the technical field of red mud resource utilization, and particularly relates to a method for recovering iron by reducing manganese-containing mineral reinforced red mud. The method comprises the following steps: 1) preparing a briquette comprising red mud, manganese-containing minerals, a binder and water; 2) drying the briquettes; 3) carrying out high-temperature oxidation consolidation on the dried blocks; 4) reducing and roasting the oxidized agglomerates with a reducing agent to obtain metallized agglomerates; 5) and (4) sequentially carrying out ore grinding and magnetic separation on the metalized agglomerates to obtain the metal iron powder. The invention utilizes manganese oxide in manganese-containing minerals to replace ferrous oxide in hercynite and fayalite, thereby leading the ferrous oxide to further participate in the reduction process; meanwhile, the manganese oxide can solidify aluminum silicon contained in the red mud in a manganese phase, so that the direct reduction effect of the red mud is enhanced, the metallization rate of the direct reduction of the red mud is improved, the growth of iron grains is promoted, the magnetic separation index is improved, and the comprehensive utilization of the red mud is promoted; meanwhile, manganese-containing minerals such as high-manganese iron ore and electrolytic manganese anode mud can be effectively utilized.
Description
Technical Field
The invention belongs to the technical field of red mud resource utilization, and particularly relates to a method for recovering iron by reducing manganese-containing mineral reinforced red mud.
Background
Red mud is a waste material produced in the industrial chain for extracting alumina. The total yield of Chinese alumina in 2019 is 7128 million tons, which accounts for about 56.6% of the total world yield, and the red mud is generated by about 1 hundred million tons. The traditional treatment method of the red mud is mainly damming and stockpiling, but the method is expensive, wastes a large amount of valuable metal elements in the red mud, and alkali and radioactive elements contained in the red mud can cause adverse effects on the environment. With the rapid development of economy in China, the steel industry continues to increase at a high speed, the demand of iron ore is rapidly increased, and under the condition that iron ore resources are increasingly reduced and tend to be exhausted, the research on the comprehensive utilization of red mud by taking the high-iron red mud as a second resource is a piece of work with strategic and practical significance.
The composition and properties of red mud are extremely complex, and the main chemical component is Fe2O3、Al2O3、SiO2、CaO、TiO2And the like, which can be used as raw materials for industrial production, wherein the iron content is relatively high and can be recycled firstly. The iron can be effectively recovered from the red mud by performing coal-based direct reduction and then performing magnetic separation, but the metallization rate of the direct reduction is low, and the recovery rate is low. Therefore, a certain amount of additives are needed in the reduction roasting process, and the additives mainly comprise magnesium salt, calcium salt, sodium salt and double salt, play a role in fluxing and improve the reduction efficiency of carbon; but the additive has larger dosage and higher cost in the using process and can cause certain environmental pollution.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a method for strengthening red mud reduction and iron recovery by manganese-containing minerals.
The technical scheme provided by the invention is as follows:
a method for recovering iron by reducing manganese-containing mineral reinforced red mud comprises the following steps:
1) preparing a briquette comprising red mud, manganese-containing minerals, a binder and water;
2) drying the briquette obtained in the step 1) to obtain a dried briquette;
3) carrying out high-temperature oxidation consolidation on the dried briquette obtained in the step 2) to obtain an oxidized briquette;
4) carrying out reduction roasting on the oxidized briquette obtained in the step 3) by using a reducing agent to obtain a metallized briquette;
5) and 4) sequentially carrying out ore grinding and magnetic separation on the metallized lumps obtained in the step 4) to obtain metal iron powder.
The ferrous oxide generated in the reduction stage of the ferric oxide in the red mud can cause reduction yield reduction due to the following reactions:
2FeO+SiO2＝Fe2SiO4
FeO+Al2O3＝FeAl2O4
in the above technical scheme, the components containing manganese minerals are added, and the following reactions can occur in the reduction stage:
2MnO+SiO2＝Mn2SiO4
MnO+Al2O3＝MnAl2O4
2MnO+Fe2SiO4＝Mn2SiO4+2FeO
MnO+FeAl2O4＝MnAl2O4+FeO
MnO+FeTiO3＝MnTiO3+FeO
2MnO+Fe2TiO4＝Mn2TiO4+2FeO
therefore, on one hand, the manganese oxide can solidify silicon oxide, aluminum oxide and the like in the red mud in the reduction stage, and the problem that the reduction yield of iron is reduced due to the combination of the manganese oxide and ferrous oxide is avoided. On the other hand, the manganese oxide can displace ferrous oxide from various iron salts in the red mud in the reduction stage, thereby increasing the reduction yield of iron.
Specifically, in step 1): uniformly mixing and agglomerating the red mud, the manganese-containing mineral, the binder and water to obtain the agglomerate, wherein the weight ratio of the red mud to the manganese-containing mineral is 12 (1-18), the percentage of the weight of the binder to the total weight of the red mud and the manganese-containing mineral is 0.1-1%, and the percentage of the weight of the water to the total weight of the red mud, the manganese-containing mineral and the binder is 10-18%.
Specifically, in step 1): the manganese-containing mineral is selected from one or more of pyrolusite, high manganese iron ore or electrolytic manganese anode mud. 55-63 wt% of manganese in pyrolusite, 8-20 wt% of manganese in high-manganese iron ore and 42-50 wt% of manganese in electrolytic manganese anode mud.
Specifically, in step 1): the binder is selected from any one or more of sodium carboxymethyl cellulose, sodium humate or polyvinyl amide.
Based on the technical scheme, compared with inorganic additives such as bentonite and the like, the various organic binders can reduce silicon-aluminum impurity elements brought by addition and hindering the direct reduction process in the high-temperature oxidation and consolidation process, and are beneficial to the direct reduction of the obtained oxidized pellets; meanwhile, the organic binder can be decomposed and volatilized in the reduction roasting process, so that gaps are generated in the oxidized pellets, and the reduction kinetic conditions of the oxidized pellets in the reduction roasting process are favorably improved, so that the direct reduction of the oxidized agglomerates is promoted.
Specifically, in the step 2): drying the briquette obtained in the step 1) for 1.5-3 hours at the temperature of 30-200 ℃ to obtain the dried briquette.
Specifically, in step 3): the temperature of the high-temperature oxidation consolidation is 950-1250 ℃; the time is 15-25 min; the atmosphere is air.
Specifically, in the step 4): the reduction roasting temperature is 1100-1350 ℃; the reduction roasting time is 40-150 min.
Specifically, in the step 4): the reducing agent is any one or mixture of more of bituminous coal, anthracite and coke; the mass ratio of carbon in the reducing agent to iron in the oxidation agglomerate is (1.5-2.5): 1.
Specifically, in step 1): and pelletizing by using a disc pelletizer or a ball press.
Specifically, in step 3): high-temperature oxidation consolidation is carried out by adopting a shaft furnace, a rotary hearth furnace, a belt type roasting machine, a chain grate machine or a rotary kiln.
Specifically, in the step 4): the raw material is roasted by a rotary kiln or a rotary hearth furnace.
Specifically, in the step 5): the magnetic separation adopts wet-type low intensity magnetic separator to carry out wet-type magnetic separation, the magnetic field intensity of wet-type magnetic separation is 0.06 ~ 0.10T, and the ore pulp concentration is 10 ~ 25 wt%.
Aiming at the problem that the reduction effect of iron is influenced by generating hercynite and fayalite in the direct reduction process of red mud, the invention replaces the ferrous oxide in hercynite and fayalite by using the manganese oxide in manganese-containing minerals, so that the ferrous oxide further participates in the reduction process; meanwhile, aluminum silicon contained in the red mud can be solidified in a manganese matter phase by the manganese oxide, so that the influence of the aluminum silicon oxide on the reduction of the iron oxide is reduced, the effect of strengthening the direct reduction of the red mud is achieved, the metallization rate of the direct reduction of the red mud can be effectively improved, the number of metal iron grains is continuously increased, the distance among monomer particles is reduced, the aggregation tendency is realized, the growth of metal iron in the pellets is promoted, the monomer dissociation in subsequent ore grinding is favorably realized, the magnetic separation index is favorably improved, and the comprehensive utilization of the red mud is promoted; meanwhile, manganese-containing minerals such as high-manganese iron ore and electrolytic manganese anode mud can be effectively utilized, the source is wide, the cost is low, the energy is saved, and the environment is protected.
Drawings
FIG. 1 is a comparative graph of the optical microscope of DRI briquettes obtained in comparative example and example 1.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Comparative example 1
For crude ore TFe content 49.11%, Al2O3Content 10.07% SiO2Uniformly mixing red mud with the content of 3.45 percent with a binder accounting for 0.5 percent of the weight of the red mud, pelletizing by using a disc pelletizer without adding manganese minerals, wherein the addition amount of water accounts for 15 percent of the mass of the uniformly mixed materials; drying at 150 deg.C for 2.5h to obtain dried lump, and subjecting the dried lump to high temperature oxidation and consolidation in a chain grate at 1050 deg.C for 15min to obtain oxidized lump; bituminous coal is used as a reducing agent, the adding amount of the reducing agent meets the mass ratio of carbon to iron of 2.0, the oxidized briquette is reduced and roasted for 120min at the temperature of 1150 ℃, the metallization rate of iron in the obtained metallized briquette is 82.91%, the magnetic separation intensity is 0.08T after ore grinding and magnetic separation, the ore pulp concentration is 15%, metal iron powder is obtained, the iron grade is 80.62%, and the iron recovery rate is 70.91%.
The DRI briquette thus obtained was tested and, as shown in part (A) of FIG. 1, the iron grains had a size of 20 to 40 μm.
Example 1
The method for recovering iron by reducing manganese-containing mineral reinforced red mud comprises the following steps:
the red mud, the manganese-containing mineral and the binder are proportioned according to a certain proportion, evenly mixed and agglomerated, and the water addition amount is 12 percent of the mass of the mixed material; drying the mass at 120 deg.C for 2.5h to obtain dried mass; carrying out high-temperature oxidation consolidation on the dried briquette to obtain an oxidized briquette; adding a certain proportion of reducing agent into the oxidized agglomerates, carrying out reduction roasting at 1150 ℃ for 150min to obtain metallized agglomerates after reduction; and grinding the metallized lumps, and magnetically separating to obtain the metal iron powder.
The manganese-containing mineral is pyrolusite;
the mass ratio of the red mud to the manganese-containing minerals is red mud: the manganese-containing mineral accounts for 12:1, and the weight percentage of the binder to the total weight of the red mud and the manganese-containing mineral is 0.2 percent;
the binder is sodium carboxymethyl cellulose;
the equipment for agglomeration is a disc pelletizer;
the high-temperature oxidation consolidation can adopt a belt type roasting machine;
the high-temperature oxidation consolidation temperature is 1050 ℃ and the time is 15 min;
the reducing agent is bituminous coal;
the addition amount of the reducing agent meets the condition that the mass ratio of carbon in the reducing agent to iron in the mixture is 2.0: 1;
the reduction roasting equipment is a rotary kiln;
the magnetic separation adopts wet-type low intensity magnetic separator to carry out wet-type magnetic separation, the magnetic field intensity of wet-type magnetic separation is 0.08T, and ore pulp concentration is 15%.
The metallization rate of the metallized lumps obtained by reduction roasting reaches 92.81%, the iron grade of the metal iron powder obtained by grinding and magnetic separation is 90.72%, and the iron recovery rate is 90.29%.
The DRI agglomerates obtained were tested, and as shown in part (B) of FIG. 1, the size of iron grains was about 30 to 60 μm, and the number of iron grains was significantly increased.
Example 2
The method for recovering iron by reducing manganese-containing mineral reinforced red mud comprises the following steps:
the red mud, the manganese-containing mineral and the binder are proportioned according to a certain proportion, evenly mixed and agglomerated, and the water addition amount is 15 percent of the mass of the mixed material; drying the block mass at 150 ℃ for 2.0h to obtain a dry block mass; carrying out high-temperature oxidation consolidation on the dried briquette to obtain an oxidized briquette; adding a certain proportion of reducing agent into the oxidized agglomerates, carrying out reduction roasting at 1200 ℃ for 100min, and obtaining metallized agglomerates after reduction; grinding the metallized lumps, and magnetically separating to obtain metal iron powder;
the manganese-containing mineral is high-manganese iron ore;
the mass ratio of the red mud to the manganese-containing minerals is red mud: the weight of the binder is 0.5 percent of the total weight of the red mud and the manganese-containing mineral;
the binder is sodium humate;
the equipment for agglomeration is a ball press;
a rotary hearth furnace is adopted for high-temperature oxidation and solidification;
the high-temperature oxidation consolidation temperature is 950 ℃, and the time is 15 min;
the reducing agent is coke;
the addition amount of the reducing agent meets the condition that the mass ratio of carbon in the reducing agent to iron in the mixture is 1.5: 1;
the reduction roasting equipment is a rotary hearth furnace;
the magnetic separation adopts wet-type low intensity magnetic separator to carry out wet-type magnetic separation, the magnetic field intensity of wet-type magnetic separation is 0.06T, and ore pulp concentration is 10%.
The metallization rate of the metallized lumps obtained by reduction roasting reaches 91.82%, the iron grade of the metal iron powder obtained by grinding and magnetic separation is 91.76%, and the iron recovery rate is 90.29%.
Example 3
The method for recovering iron by reducing manganese-containing mineral reinforced red mud comprises the following steps:
the red mud, the manganese-containing mineral and the binder are proportioned according to a certain proportion, evenly mixed and agglomerated, and the water addition amount is 18 percent of the mass of the mixed material; drying the block mass for 1.5h at 200 ℃ to obtain a dry block mass; carrying out high-temperature oxidation consolidation on the dried briquette to obtain an oxidized briquette; adding a certain proportion of reducing agent into the oxidized agglomerates, carrying out reduction roasting at 1100 ℃ for 150min to obtain metallized agglomerates after reduction; grinding the metallized lumps, and magnetically separating to obtain metal iron powder;
the manganese-containing mineral is high-manganese iron ore;
the mass ratio of the red mud to the manganese-containing minerals is red mud: the weight of the binder is 1 percent of the total weight of the red mud and the manganese-containing mineral;
the binder is polyvinyl amide;
the equipment for agglomeration is a ball press;
the high-temperature oxidation consolidation can adopt a shaft furnace;
the high-temperature oxidation consolidation temperature is 1150 ℃ and the time is 20 min;
the reducing agent is anthracite;
the addition amount of the reducing agent meets the condition that the mass ratio of carbon in the reducing agent to iron in the mixture is 2.0: 1;
the reduction roasting equipment is a rotary kiln;
the magnetic separation adopts wet-type low intensity magnetic separator to carry out wet-type magnetic separation, the magnetic field intensity of wet-type magnetic separation is 0.10T, and ore pulp concentration is 20%.
The metallization rate of the metallized lumps obtained by reduction roasting reaches 90.43%, the iron grade of the metal iron powder obtained by grinding and magnetic separation is 88.35%, and the iron recovery rate is 87.82%.
Example 4
The method for recovering iron by reducing the manganese-containing mineral reinforced red mud comprises the following steps:
the red mud, the manganese-containing mineral and the binder are proportioned according to a certain proportion, evenly mixed and agglomerated, and the water addition amount is 10 percent of the mass of the mixed material; drying the block mass at 160 ℃ for 2.0h to obtain a dried block mass; carrying out high-temperature oxidation consolidation on the dried briquette to obtain an oxidized briquette; adding a certain proportion of reducing agent into the oxidized briquette, carrying out reduction roasting at 1350 ℃ for 50min to obtain a metallized briquette after the reduction is finished; grinding the metallized lumps, and magnetically separating to obtain metal iron powder;
the manganese-containing mineral is electrolytic manganese anode mud, electrolytic manganese anode mud and the like;
the mass ratio of the red mud to the manganese-containing minerals is red mud: the manganese-containing mineral accounts for 12:4, and the weight of the binder is 0.8 percent of the total weight of the red mud and the manganese-containing mineral;
the binder is polyvinyl amide;
the equipment for agglomeration is a disc pelletizer;
adopting a chain grate machine for high-temperature oxidation and solidification;
the high-temperature oxidation consolidation temperature is 1200 ℃, and the time is 25 min;
the reducing agent is bituminous coal;
the addition amount of the reducing agent meets the condition that the mass ratio of carbon in the reducing agent to iron in the mixture is 2.5: 1;
the reduction roasting equipment is a rotary kiln;
the magnetic separation adopts wet-type low intensity magnetic separator to carry out wet-type magnetic separation, the magnetic field intensity of wet-type magnetic separation is 0.06T, and ore pulp concentration is 20%.
The metallization rate of the metallized lumps obtained by reduction roasting reaches 93.36 percent, the iron grade of the metal iron powder obtained by grinding and magnetic separation is 92.27 percent, and the iron recovery rate is 91.32 percent.
Aiming at the problem that the reduction effect of iron is influenced by generating hercynite and fayalite in the direct reduction process of red mud, the method utilizes manganese oxide in manganese-containing minerals to replace ferrous oxide in hercynite and fayalite, so that the ferrous oxide further participates in the reduction process; meanwhile, the manganese oxide can solidify aluminum silicon contained in the red mud in a manganese material phase, and the influence of the aluminum silicon oxide on the reduction of the iron oxide is reduced, so that the effect of strengthening the direct reduction of the red mud is achieved, the metallization rate of the direct reduction of the red mud can be effectively improved, the growth of iron grains is promoted, the magnetic separation index is favorably improved, the comprehensive utilization of the red mud is promoted, the energy is saved, and the environment is protected.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A method for recovering iron by reducing manganese-containing mineral reinforced red mud is characterized by comprising the following steps:
1) preparing a briquette comprising red mud, manganese-containing minerals, a binder and water;
2) drying the briquette obtained in the step 1) to obtain a dried briquette;
3) carrying out high-temperature oxidation consolidation on the dried briquette obtained in the step 2) to obtain an oxidized briquette;
4) carrying out reduction roasting on the oxidized briquette obtained in the step 3) by using a reducing agent to obtain a metallized briquette;
5) and 4) sequentially carrying out ore grinding and magnetic separation on the metallized lumps obtained in the step 4) to obtain metal iron powder.
2. The method for recovering iron by reducing manganese-containing mineral reinforced red mud according to claim 1, wherein in the step 1): uniformly mixing and agglomerating the red mud, the manganese-containing mineral, the binder and water to obtain the agglomerate, wherein the weight ratio of the red mud to the manganese-containing mineral is 12 (1-18), the percentage of the weight of the binder to the total weight of the red mud and the manganese-containing mineral is 0.1-1%, and the percentage of the weight of the water to the total weight of the red mud, the manganese-containing mineral and the binder is 10-18%.
3. The method for recovering iron by reducing manganese-containing mineral reinforced red mud according to claim 1 or 2, wherein in the step 1):
the manganese-containing mineral is selected from one or more of pyrolusite, high manganese iron ore or electrolytic manganese anode mud;
the binder is selected from any one or more of sodium carboxymethyl cellulose, sodium humate or polyvinyl amide.
4. The method for recovering iron by reducing manganese-containing mineral reinforced red mud according to claim 1, wherein in the step 2): drying the briquette obtained in the step 1) for 1.5-3 hours at the temperature of 30-200 ℃ to obtain the dried briquette.
5. The method for recovering iron by reducing manganese-containing mineral reinforced red mud according to claim 1, wherein in the step 3): the temperature of the high-temperature oxidation consolidation is 950-1250 ℃; the time is 15-25 min; the atmosphere is air.
6. The method for recovering iron by reducing manganese-containing mineral reinforced red mud according to claim 1, wherein in the step 3): high-temperature oxidation consolidation is carried out by adopting a shaft furnace, a rotary hearth furnace, a belt type roasting machine, a chain grate machine or a rotary kiln.
7. The method for recovering iron by reducing manganese-containing mineral reinforced red mud according to claim 1, wherein in the step 4): the reduction roasting temperature is 1100-1350 ℃; the reduction roasting time is 40-150 min.
8. The method for recovering iron by reducing manganese-containing mineral reinforced red mud according to claim 1, wherein in the step 4):
the reducing agent is any one or mixture of more of bituminous coal, anthracite and coke;
the mass ratio of carbon in the reducing agent to iron in the oxidation agglomerate is (1.5-2.5): 1.
9. The method for recovering iron by reducing manganese-containing mineral reinforced red mud according to claim 1, wherein in the step 4): the raw material is roasted by a rotary kiln or a rotary hearth furnace.
10. The method for recovering iron by reducing manganese-containing mineral reinforced red mud according to any one of claims 1 to 9, wherein in the step 5): the magnetic separation adopts wet-type low intensity magnetic separator to carry out wet-type magnetic separation, the magnetic field intensity of wet-type magnetic separation is 0.06 ~ 0.10T, and the ore pulp concentration is 10 ~ 25 wt%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113999947A (en) * | 2021-11-02 | 2022-02-01 | 武汉科技大学 | Additive for separating slag iron of high-aluminum iron ore smelting and separation method |
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