CN105907948B - The method of the low-grade magnetic separation of metallized pellet containing chromic vanadium-titanium ferroferrite separation - Google Patents
The method of the low-grade magnetic separation of metallized pellet containing chromic vanadium-titanium ferroferrite separation Download PDFInfo
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- CN105907948B CN105907948B CN201610486319.9A CN201610486319A CN105907948B CN 105907948 B CN105907948 B CN 105907948B CN 201610486319 A CN201610486319 A CN 201610486319A CN 105907948 B CN105907948 B CN 105907948B
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C1/00—Magnetic separation
- B03C1/02—Magnetic separation acting directly on the substance being separated
-
- 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
- C22B1/243—Binding; Briquetting ; Granulating with binders inorganic
Abstract
A kind of method of the low-grade magnetic separation of metallized pellet containing chromic vanadium-titanium ferroferrite separation, the non-technical field of blast furnace process belonged in the low-grade method of comprehensive utilization of powder containing chromic vanadium-titanium ferroferrite.This method is carried out according to the following steps：(1) low-grade powder containing chromic vanadium-titanium ferroferrite, reduction coal dust, binding agent and additive are weighed and carries out batch mixing；(2) by mixed material, pelletizing is made, dries；(3) pelletizing of drying is subjected to coal base pelletizing autoreduction high-temperature roasting；(4) metallized pellet of high-temperature roasting is cooled down；(5) by the metallized pellet of cooling, crush, obtain metallized pellet powder, then carry out magnetic separation separation with magnetic separation tube, obtain the Magnetic Materials rich in iron and the nonmagnetics rich in titanium.This method causes strategy metal vanadium, titanium, the utilization rate of chromium to reach maximization on the premise of improving this low-grade coal of pelletizing containing chromic vanadium-titanium ferroferrite base and strengthening the degree of metalization of reduction, iron recovery.
Description
Technical field
The invention belongs to the non-technical field of blast furnace process in the low-grade method of comprehensive utilization of powder containing chromic vanadium-titanium ferroferrite,
The method of the more particularly to low-grade magnetic separation of metallized pellet containing chromic vanadium-titanium ferroferrite separation.
Background technology
V-ti magnetite miberal powder is a kind of more metal intergrowth minerals rich in a variety of valuable constituent elements such as iron, vanadium, titanium, application value
It is high.It is comparatively ripe to common vanadium titano-magnetite research at present, but the research containing chromic vanadium-titanium ferroferrite is still needed to
Further systematization, and high-grade is concentrated mainly on to the research containing chromic vanadium-titanium ferroferrite and contains chromic vanadium-titanium ferroferrite, and it is right
The low-grade research containing chromic vanadium-titanium ferroferrite is still more deficient, and further development is needed in its correlative study work badly.
Recently as the fast development of China's steel industry, supply falls short of demand for domestic Iron Ore Market, low-grade iron ore powder
Resource has the demand for being produced and utilizing, economic benefit is expected to significantly, and low product as a kind of Iron Ore Powder resource for having Exploitative potential
Position powder containing chromic vanadium-titanium ferroferrite is the high low-grade iron ore powder resource of one of which extraction value, and its strategy being rich in is golden
Category chromium, vanadium, titanium are expected to synchronously efficiently be utilized, therefore are sent to great expectations.
In order to alleviate blast furnace ironmaking cost in increased nervous situation year by year, people constantly explore and research and develop blast furnace ironmaking with
Outer new technology and new technology, therefore non-blast furnace ironmaking has turned into the focus of a research, rather than coal base is directly gone back in blast furnace process
There is original-magnetic separation separating technology the advantage that flow is short, energy consumption is low, cost is low to be expected to expanded use.
In order to preferably carry out the research work of the low-grade powder containing chromic vanadium-titanium ferroferrite, the low-grade titanium of vanadium containing chromium type is formed
The theoretical system of magnetite powder, the ironmaking work in more preferable Instructing manufacture practice.The present invention utilizes Liaoning Ka Zuo somewheres still
Raw material based on the low-grade powder containing chromic vanadium-titanium ferroferrite that non-large scale mining utilizes, a kind of low-grade vanadium containing chromium type is invented
The method of titanomagnetite metallized pellet magnetic separation separation.
The content of the invention
Resources characteristic for the low-grade powder containing chromic vanadium-titanium ferroferrite and its study application field in non-blast furnace ironmaking
The blank of aspect, the present invention provide a kind of method of the low-grade magnetic separation of metallized pellet containing chromic vanadium-titanium ferroferrite separation, the party
Method strengthens the premise of the degree of metalization of reduction, iron recovery improving this low-grade coal of pelletizing containing chromic vanadium-titanium ferroferrite base
Under, while cause strategy metal vanadium, titanium, the utilization rate of chromium to reach maximization.
The method of the low-grade magnetic separation of metallized pellet containing the chromic vanadium-titanium ferroferrite separation of the present invention, enters according to the following steps
OK：
Step 1, batch mixing：
Weigh low-grade powder containing chromic vanadium-titanium ferroferrite, reduction coal dust, binding agent and additive and carry out batch mixing, mixing is made
Material；Wherein, additive B2O3、Na2CO3、CaF2、Na2SO4Or CaCO3In one kind, reduce the carbon and low-grade in coal dust
The oxygen of ferriferous oxide in powder containing chromic vanadium-titanium ferroferrite, by carbon-to-oxygen ratio (C/O)=1.1~1.4, binder content is mixed material
The 1~2% of quality, additive level are the 0~8% of mixed material quality；
Step 2, pelletizing：
(1) to mixed material, water is added, mixing, boils in a covered pot over a slow fire 30~40min of material；Wherein, in mass ratio, added in mixed material
The amount of water：Mixed material=8~11%；
(2) material boiled in a covered pot over a slow fire is subjected to pelletizing, in balling process, adds water, granularity is made and contains chromium for the low-grade of 7~16mm
Type V-ti Bearing Magnetite Pellets, wherein, in obtained low-grade pelletizing containing chromic vanadium-titanium ferroferrite, the weight content of water for 9~
12%；
(3) low-grade pelletizing containing chromic vanadium-titanium ferroferrite is put into oven for drying, the pelletizing dried；
Step 3, it is calcined：
(1) the pelletizing embedment of drying is filled into the graphite crucible of lump coal, be put into high temperature box furnace；
(2) coal base pelletizing autoreduction high-temperature calcination process is：Under argon gas or nitrogen protection atmosphere, high temperature box furnace is with 8
~12 DEG C/min programming rate, from room temperature to 1275~1325 DEG C, 15~45min of high-temperature roasting, obtain high-temperature roasting
Metallized pellet；
(3) by the metallized pellet of high-temperature roasting, room temperature is cooled to, the metallized pellet cooled down；
Step 4, magnetic separation separates
(1) by the metallized pellet of cooling, crush, obtain the metallized pellet powder that granularity is less than 200 mesh；
(2) magnetic separation separation is carried out to metallized pellet powder with the magnetic separation tube that magnetic field intensity is 130~200kA/m, obtains richness
The Magnetic Materials of iron content and the nonmagnetics rich in titanium.
Wherein,
In the step 1, the TFe of the described low-grade powder containing chromic vanadium-titanium ferroferrite is 43.0~45.0wt.%, comprising
Chemical composition and its percentage by weight be Fe3O4：40.0~42.7%, FeO：17.0~19.0%, CaO：3.0~4.0%,
SiO2：6.5~7.5%, MgO：0.6~0.8%, Al2O3：1.5~2.1%, TiO2：20.0~22.0%, V2O5：1.6~
1.8%, Cr2O3：0.02~0.2%, S≤0.05%, P≤0.01%, surplus are inevitable impurity.
In the step 1, in described low-grade powder containing chromic vanadium-titanium ferroferrite, the part below the mesh of granularity 200 accounts for always
More than the 70% of weight, the part below 100 mesh account for more than the 95% of gross weight.
In the step 1, described reduction coal dust, particle mean size below 200 mesh, reduce the volatile content of coal dust compared with
Height, content of ashes are relatively low.
In the step 1, described binding agent is bentonite, and particle mean size is below 200 mesh.
In the step 1, described carbon-to-oxygen ratio calculation formula is：
C/o=[mcoal×wc)/Mc]/{[mors×(wO, Fe2O3+wO, FeO)]/Mo}
Wherein, mcoal：Reduce the quality (g) of coal dust, more：The quality (g) of the low-grade powder containing chromic vanadium-titanium ferroferrite, wc：
Reduce the fixation carbon content (%) of coal dust, wO, Fe2O3：Fe2O3The percentage (%) of middle oxygen, wO, FeO：The percentage of oxygen in FeO
(%), Mc：The molal weight (g/mol) of carbon, Mo：The molal weight (g/mol) of oxygen.
Wherein,
In mass ratio, coal dust is reduced：Low-grade powder containing chromic vanadium-titanium ferroferrite=4.66~3.66.
In the step 1, experimental facilities used in batch mixing is ball mill, and mixing time is more than or equal to 4h.
In the step 2 (1), it is balling disk (-sc) that pelletizing, which prepares device therefor, and balling disk (-sc) rotating speed is in 17~19r/min.
In the step 2 (3), the low-grade drying time of pelletizing containing chromic vanadium-titanium ferroferrite is more than or equal to 5h.
In the step 3 (1), described lump coal particle mean size is 0.6~3mm.
In the step 3 (2), roasting process is carried out under argon gas or nitrogen protection atmosphere, prevents the pelletizing of reduction from occurring
Reoxidize.
Described step 3 (2), to carry out coal base pelletizing autoreduction high-temperature calcination process to pelletizing.
In the step 3 (3), the type of cooling is buries coal spontaneous cooling, argon gas atmosphere cooling, nitrogen atmosphere cools down or water quenching
One kind in cooling.
In the step 4 (1), it is sealed type sample pulverizer to crush equipment used.
In the step 4 (2), it is TFe that Magnetic Materials, which include composition and its mass percent,：70.43~81.44%, MFe：
68.16~75.80%, V：1.15~1.40%, Cr are 0.034~0.045%, TiO2：7.96~11.04%, nonmagnetics
It is TFe comprising composition and its mass percent：4.75~10.24%, TiO2：37.43~42.21%, V：0.32~0.63%,
Cr<0.01%.
In the step 4 (2), iron recovery reaches 88~98%, the part in vanadium enrichment to Magnetic Materials>74%, chromium is rich
Collect the part in Magnetic Materials>85%, titanium is enriched to the part in nonmagnetics>68%.
The degree of metalization of the low-grade pelletizing containing chromic vanadium-titanium ferroferrite of the present invention reaches more than 90%.
The method of the low-grade magnetic separation of metallized pellet containing the chromic vanadium-titanium ferroferrite separation of the present invention, compared to existing skill
Art, its advantage are：Take full advantage of the low-grade resource of powder containing chromic vanadium-titanium ferroferrite, greatly enhance iron, chromium,
The valuable constituent element utilization rate such as vanadium, titanium；The metallized pellet magnetic separation separating technology flow is short, simple to operate, and coal in technical process
Powder instead of coke, reduce energy consumption, save cost；The additive B of addition2O3, Na2CO3, CaF2, Na2SO4, CaCO3It is beneficial to
Promote the reduction of the low-grade powder containing chromic vanadium-titanium ferroferrite and growing up for iron granule, and then beneficial to the separation of slag iron；Reduction
The type of cooling that sample after roasting uses, can effectively prevent that going back original sample reoxidizes, and ensures the gold of metallized pellet
Between category rate reaches 90~99.85%, iron recovery reaches 88~98%；Magnetic separation is except the raising beneficial to iron recovery, together
When also help the enrichment and recycling of valuable constituent element vanadium, chromium and titanium, the part in vanadium enrichment to Magnetic Materials>74%, chromium is rich
Collect the part in Magnetic Materials>85%, titanium is enriched to the part in nonmagnetics>68%.The present invention contains chromium type using low-grade
V-ti Bearing Magnetite Pellets preparation technology, enterprises production locale requirement can be met.
Brief description of the drawings
Fig. 1 is the technological process of the method for the low-grade magnetic separation of metallized pellet containing the chromic vanadium-titanium ferroferrite separation of the present invention
Figure；
Fig. 2 is the ore deposit phasor for the metallized pellet that the embodiment of the present invention 3 obtains；(a) 200 times are amplified；(b) 5000 are amplified
Times；
Fig. 3 is the XRD spectrum for the metallized pellet that the embodiment of the present invention 3 obtains；
Fig. 4 is the XRD spectrum for the magnetic product that the embodiment of the present invention 3 obtains；
Fig. 5 is the XRD spectrum for the non magnetic product that the embodiment of the present invention 3 obtains.
Embodiment
The low-grade powder containing chromic vanadium-titanium ferroferrite of the embodiment of the present invention comes from Liaoning Ka Zuo somewheres.
The TFe for the low-grade powder containing chromic vanadium-titanium ferroferrite selected in the embodiment of the present invention is 43.0~45.0wt.%, bag
The chemical composition and its percentage by weight contained is Fe3O4：40.0~42.7%, FeO：17.0~19.0%, CaO：3.0~
4.0%, SiO2：6.5~7.5%, MgO：0.6~0.8%, Al2O3：1.5~2.1%, TiO2：20.0~22.0%, V2O5：
1.6~1.8%, Cr2O3：0.02~0.2%, S≤0.05%, P≤0.01%, surplus are inevitable impurity.
The bentonite of the embodiment of the present invention is commercial products.
The additive B used in the embodiment of the present invention2O3, Na2CO3, CaF2, Na2SO4, CaCO3For commercial products, granularity
Part below 200 mesh accounts for more than the 50% of gross weight, and purity is >=98%.
Present invention process is described further with reference to the accompanying drawings and examples.
The process chart that the embodiment of the present invention uses is as shown in Figure 1.
Embodiment 1
A kind of method of the low-grade magnetic separation of metallized pellet containing chromic vanadium-titanium ferroferrite separation, is carried out according to the following steps：
Step 1, batch mixing：
Weigh low-grade powder containing chromic vanadium-titanium ferroferrite, reduction coal dust, bentonite to be put into ball mill, carry out batch mixing, mix
The material time is 4h, and mixed material is made；Wherein, iron in carbon and low-grade powder containing chromic vanadium-titanium ferroferrite in coal dust is reduced to aoxidize
The oxygen of thing, by carbon-to-oxygen ratio (C/O)=1.2, i.e., in mass ratio, low-grade powder containing chromic vanadium-titanium ferroferrite：Coal dust=4.27 are reduced,
Bentonite content is the 2% of mixed material quality；
Step 2, pelletizing：
(1) to mixed material, water is added, mixing, boils in a covered pot over a slow fire material 40min；Wherein, in mass ratio, water is added in mixed material
Amount：Mixed material=8%；
(2) material that will have been boiled in a covered pot over a slow fire, it is put into the balling disk (-sc) that rotating speed is 17r/min, progress pelletizing, in balling process, adds water,
The low-grade pelletizing containing chromic vanadium-titanium ferroferrite that granularity is 8~12mm is made, wherein, obtained low-grade v-ti magnetite containing chromium type
In ore deposit pelletizing, the weight content of water is 9%；
(3) low-grade pelletizing containing chromic vanadium-titanium ferroferrite is put into baking oven 5h, dried, the pelletizing dried；
Step 3, it is calcined：
(1) the pelletizing embedment of drying is filled into the graphite crucible that particle mean size is 0.6~3mm lump coal, is put into high-temperature box type
In stove；
(2) coal base pelletizing autoreduction high-temperature calcination process is：Under argon atmosphere, high temperature box furnace is with 8 DEG C/min
Programming rate, from room temperature to 1300 DEG C, high-temperature roasting 30min, obtain the metallized pellet of high-temperature roasting；
(3) metallized pellet of high-temperature roasting is taken out from high temperature box furnace, buries coal spontaneous and be cooled to room temperature, obtained cold
But metallized pellet, the degree of metalization for measuring the low-grade pelletizing containing chromic vanadium-titanium ferroferrite are 99.13%；
Step 4, magnetic separation separates
(1) metallized pellet of cooling is put into sealed type sample pulverizer, crushes, obtain granularity and be less than 200 purposes
Metallized pellet powder；
(2) magnetic separation separation is carried out to metallized pellet powder with the magnetic separation tube that magnetic field intensity is 180kA/m, obtained rich in iron
Magnetic Materials and the nonmagnetics rich in titanium, wherein, the composition and its mass percent that Magnetic Materials include are that TFe is 76.57%,
MFe is 75.80%, V 1.33%, Cr 0.041%, TiO2For 10.40%, the composition and its quality hundred that nonmagnetics includes
It is that TFe is 5.38% to divide ratio, TiO2For 42.21%, V 0.49%, Cr<0.0068%, the rate of recovery of wherein iron is
88.31%, vanadium has in 82.85% entrance Magnetic Materials, and chromium has 90.92% to enter in Magnetic Materials, and titanium has 70.12% entrance non magnetic
In thing.
Embodiment 2
A kind of method of the low-grade magnetic separation of metallized pellet containing chromic vanadium-titanium ferroferrite separation, is carried out according to the following steps：
Step 1, batch mixing：
Weigh low-grade powder containing chromic vanadium-titanium ferroferrite, reduction coal dust, bentonite to be put into ball mill, carry out batch mixing, mix
The material time is 5h, and mixed material is made；Wherein, iron in carbon and low-grade powder containing chromic vanadium-titanium ferroferrite in coal dust is reduced to aoxidize
The oxygen of thing, by carbon-to-oxygen ratio (C/O)=1.1, i.e., in mass ratio, low-grade powder containing chromic vanadium-titanium ferroferrite：Coal dust=4.66 are reduced,
Bentonite content is the 1.5% of mixed material quality；
Step 2, pelletizing：
(1) to mixed material, water is added, mixing, boils in a covered pot over a slow fire material 30min；Wherein, in mass ratio, water is added in mixed material
Amount：Mixed material=9%；
(2) material that will have been boiled in a covered pot over a slow fire, it is put into the balling disk (-sc) that rotating speed is 19r/min, progress pelletizing, in balling process, adds water,
The low-grade pelletizing containing chromic vanadium-titanium ferroferrite that granularity is 7~10mm is made, wherein, obtained low-grade v-ti magnetite containing chromium type
In ore deposit pelletizing, the weight content of water is 10%；
(3) low-grade pelletizing containing chromic vanadium-titanium ferroferrite is put into baking oven 5.5h, dried, the pelletizing dried；
Step 3, it is calcined：
(1) the pelletizing embedment of drying is filled into the graphite crucible that particle mean size is 0.6~3mm lump coal, is put into high-temperature box type
In stove；
(2) coal base pelletizing autoreduction high-temperature calcination process is：Under argon atmosphere, high temperature box furnace is with 12 DEG C/min
Programming rate, from room temperature to 1275 DEG C, high-temperature roasting 45min, obtain the metallized pellet of high-temperature roasting；
(3) metallized pellet of high-temperature roasting is taken out from high temperature box furnace, argon gas atmosphere is cooled to room temperature, obtains cold
But metallized pellet, the degree of metalization for measuring the low-grade pelletizing containing chromic vanadium-titanium ferroferrite are 97.11%；
Step 4, magnetic separation separates
(1) metallized pellet of cooling is put into sealed type sample pulverizer, crushes, obtain granularity and be less than 200 purposes
Metallized pellet powder；
(2) magnetic separation separation is carried out to metallized pellet powder with the magnetic separation tube that magnetic field intensity is 130kA/m, obtained rich in iron
Magnetic Materials and the nonmagnetics rich in titanium, wherein, the composition and its mass percent that Magnetic Materials include are that TFe is 72.11%,
MFe is 70.23%, V 1.20%, Cr 0.045%, TiO2For 10.79%, the composition and its quality hundred that nonmagnetics includes
It is that TFe is 5.98% to divide ratio, TiO2For 40.22%, V 0.61%, Cr is<0.01%, the rate of recovery of wherein iron is
91.20%, vanadium has in 77.72% entrance Magnetic Materials, and chromium has 88.86% to enter in Magnetic Materials, and titanium has 68.01% entrance non magnetic
In thing.
Embodiment 3
A kind of method of the low-grade magnetic separation of metallized pellet containing chromic vanadium-titanium ferroferrite separation, is carried out according to the following steps：
Step 1, batch mixing：
Weigh low-grade powder containing chromic vanadium-titanium ferroferrite, reduction coal dust, bentonite and CaF2It is put into ball mill, is mixed
Material, mixing time 5h, mixed material is made；Wherein, reduce in the carbon and low-grade powder containing chromic vanadium-titanium ferroferrite in coal dust
The oxygen of ferriferous oxide, by carbon-to-oxygen ratio (C/O)=1.2, i.e., in mass ratio, low-grade powder containing chromic vanadium-titanium ferroferrite：Reduce coal dust
=4.27, bentonite content is 2%, CaF of mixed material quality2Content is the 8% of total mixture material；
Step 2, pelletizing：
(1) to mixed material, water is added, mixing, boils in a covered pot over a slow fire material 30min；Wherein, in mass ratio, water is added in mixed material
Amount：Mixed material=9%；
(2) material that will have been boiled in a covered pot over a slow fire, it is put into the balling disk (-sc) that rotating speed is 17r/min, progress pelletizing, in balling process, adds water,
The low-grade pelletizing containing chromic vanadium-titanium ferroferrite that granularity is 10~13mm is made, wherein, the obtained low-grade titanium of vanadium containing chromium type magnetic
In iron ore pellets, the weight content of water is 9%；
(3) low-grade pelletizing containing chromic vanadium-titanium ferroferrite is put into baking oven 5.5h, dried, the pelletizing dried；
Step 3, it is calcined：
(1) the pelletizing embedment of drying is filled into the graphite crucible that particle mean size is 0.6~3mm lump coal, is put into high-temperature box type
In stove；
(2) coal base pelletizing autoreduction high-temperature calcination process is：Under argon atmosphere, high temperature box furnace is with 10 DEG C/min
Programming rate, from room temperature to 1300 DEG C, high-temperature roasting 30min, obtain the metallized pellet of high-temperature roasting；
(3) metallized pellet of high-temperature roasting is taken out from high temperature box furnace, nitrogen atmosphere is cooled to room temperature, obtains cold
But metallized pellet, the degree of metalization for measuring the low-grade pelletizing containing chromic vanadium-titanium ferroferrite are 98.91%；
Step 4, magnetic separation separates
(1) metallized pellet of cooling is put into sealed type sample pulverizer, crushes, obtain granularity and be less than 200 purposes
Metallized pellet powder；
(2) magnetic separation separation is carried out to metallized pellet powder with the magnetic separation tube that magnetic field intensity is 160kA/m, obtained rich in iron
Magnetic Materials and the nonmagnetics rich in titanium, wherein, the composition and its mass percent that Magnetic Materials include are：TFe is 77.36%,
MFe is 72.88%, V 1.40%, Cr 0.034%, TiO2For 7.96%, the composition and its quality hundred that nonmagnetics includes
Point ratio is：TFe is 4.75%, TiO2For 39.35%, V 0.32%, Cr is<0.0068%, the rate of recovery of wherein iron is
92.10%, vanadium has in 83.72% entrance Magnetic Materials, and chromium has 85.21% to enter in Magnetic Materials, and titanium has 80.79% entrance non magnetic
In thing.
Wherein, the ore deposit phasor of the metallized pellet obtained is as shown in Fig. 2 wherein, (a) is 200 times of amplification；(b) it is amplification
5000 times, white portion corresponding to A is metal iron phase in (b), and dark gray section corresponding to B is TiO2Phase, remaining black are mutually led
It to be gangue phase；The XRD spectrum of obtained metallized pellet is as shown in Figure 3；The XRD spectrum of obtained magnetic product is shown in Fig. 4；
To the XRD spectrum of non magnetic product see Fig. 5.
Embodiment 4
A kind of method of the low-grade magnetic separation of metallized pellet containing chromic vanadium-titanium ferroferrite separation, is carried out according to the following steps：
Step 1, batch mixing：
Weigh low-grade powder containing chromic vanadium-titanium ferroferrite, reduction coal dust, bentonite and Na2CO3It is put into ball mill, carries out
Batch mixing, mixing time 5h, mixed material is made；Wherein, carbon and the low-grade powder containing chromic vanadium-titanium ferroferrite in coal dust are reduced
The oxygen of middle ferriferous oxide, by carbon-to-oxygen ratio (C/O)=1.4, i.e., in mass ratio, low-grade powder containing chromic vanadium-titanium ferroferrite：Reduction coal
Powder=3.66, bentonite content are 1%, Na of mixed material quality2CO3Content is the 4% of total mixture material；
Step 2, pelletizing：
(1) to mixed material, water is added, mixing, boils in a covered pot over a slow fire material 30min；Wherein, in mass ratio, water is added in mixed material
Amount：Mixed material=11%；
(2) material that will have been boiled in a covered pot over a slow fire, it is put into the balling disk (-sc) that rotating speed is 18r/min, progress pelletizing, in balling process, adds water,
The low-grade pelletizing containing chromic vanadium-titanium ferroferrite that granularity is 12~16mm is made, wherein, the obtained low-grade titanium of vanadium containing chromium type magnetic
In iron ore pellets, the weight content of water is 12%；
(3) low-grade pelletizing containing chromic vanadium-titanium ferroferrite is put into baking oven 5h, dried, the pelletizing dried；
Step 3, it is calcined：
(1) the pelletizing embedment of drying is filled into the graphite crucible that particle mean size is 0.6~3mm lump coal, is put into high-temperature box type
In stove；
(2) coal base pelletizing autoreduction high-temperature calcination process is：Under argon atmosphere, high temperature box furnace is with 8 DEG C/min
Programming rate, from room temperature to 1325 DEG C, high-temperature roasting 15min, obtain the metallized pellet of high-temperature roasting；
(3) metallized pellet of high-temperature roasting is taken out from high temperature box furnace, water quenching cooling to room temperature, is then placed in baking
In case, vacuum drying is carried out, the metallized pellet cooled down, measures the metallization of the low-grade pelletizing containing chromic vanadium-titanium ferroferrite
Rate is 98.76%；
Step 4, magnetic separation separates
(1) metallized pellet of cooling is put into sealed type sample pulverizer, crushes, obtain granularity and be less than 200 purposes
Metallized pellet powder；
(2) magnetic separation separation is carried out to metallized pellet powder with the magnetic separation tube that magnetic field intensity is 200kA/m, obtained rich in iron
Magnetic Materials and the nonmagnetics rich in titanium, wherein, the composition and its mass percent that Magnetic Materials include are that TFe is 81.44%,
MFe is 74.60%, V 1.33%, Cr 0.044%, TiO2For 9.78%, the composition and its quality hundred that nonmagnetics includes
It is that TFe is 10.24% to divide ratio, TiO2For 41.02%, V 0.63%, Cr 0.0064%, wherein the iron rate of recovery are
97.19%, vanadium has in 76.74% entrance Magnetic Materials, and chromium has 91.46% to enter in Magnetic Materials, and titanium has 73.03% entrance non magnetic
In thing.
Embodiment 5
A kind of method of the low-grade magnetic separation of metallized pellet containing chromic vanadium-titanium ferroferrite separation, is carried out according to the following steps：
Step 1, batch mixing：
Weigh low-grade powder containing chromic vanadium-titanium ferroferrite, reduction coal dust, bentonite and B2O3It is put into ball mill, is mixed
Material, mixing time 5h, mixed material is made；Wherein, reduce in the carbon and low-grade powder containing chromic vanadium-titanium ferroferrite in coal dust
The oxygen of ferriferous oxide, by carbon-to-oxygen ratio (C/O)=1.2, i.e., in mass ratio, low-grade powder containing chromic vanadium-titanium ferroferrite：Reduce coal dust
=4.27, bentonite content is 2%, B of mixed material quality2O3Content is the 8% of total mixture material；
Step 2, pelletizing：
(1) to mixed material, water is added, mixing, boils in a covered pot over a slow fire material 30min；Wherein, in mass ratio, water is added in mixed material
Amount：Mixed material=11%；
(2) material that will have been boiled in a covered pot over a slow fire, it is put into the balling disk (-sc) that rotating speed is 17r/min, progress pelletizing, in balling process, adds water,
The low-grade pelletizing containing chromic vanadium-titanium ferroferrite that granularity is 9~12mm is made, wherein, obtained low-grade v-ti magnetite containing chromium type
In ore deposit pelletizing, the weight content of water is 12%；
(3) low-grade pelletizing containing chromic vanadium-titanium ferroferrite is put into baking oven 5h, dried, the pelletizing dried；
Step 3, it is calcined：
(1) the pelletizing embedment of drying is filled into the graphite crucible that particle mean size is 0.6~3mm lump coal, is put into high-temperature box type
In stove；
(2) coal base pelletizing autoreduction high-temperature calcination process is：Under argon atmosphere, high temperature box furnace is with 12 DEG C/min
Programming rate, from room temperature to 1300 DEG C, high-temperature roasting 30min, obtain the metallized pellet of high-temperature roasting；
(3) metallized pellet of high-temperature roasting is taken out from high temperature box furnace, buries coal spontaneous and be cooled to room temperature, obtained cold
But metallized pellet, the degree of metalization for measuring the low-grade pelletizing containing chromic vanadium-titanium ferroferrite are 99.34%；
Step 4, magnetic separation separates
(1) metallized pellet of cooling is put into sealed type sample pulverizer, crushes, obtain granularity and be less than 200 purposes
Metallized pellet powder；
(2) magnetic separation separation is carried out to metallized pellet powder with the magnetic separation tube that magnetic field intensity is 160kA/m, obtained rich in iron
Magnetic Materials and the nonmagnetics rich in titanium, wherein, the composition and its mass percent that Magnetic Materials include are that TFe is 70.43%,
MFe is 68.16%, V 1.23%, Cr 0.044%, TiO2For 10.59%, the composition and its quality hundred that nonmagnetics includes
It is that TFe is 6.92% to divide ratio, TiO2For 41.82%, V 0.49%, Cr is<0.0068%, the rate of recovery of wherein iron is
95.94%, vanadium has in 83.80% entrance Magnetic Materials, and chromium has 92.85% to enter in Magnetic Materials, and titanium has 68.01% entrance non magnetic
In thing.
Embodiment 6
A kind of method of the low-grade magnetic separation of metallized pellet containing chromic vanadium-titanium ferroferrite separation, is carried out according to the following steps：
Step 1, batch mixing：
Weigh low-grade powder containing chromic vanadium-titanium ferroferrite, reduction coal dust, bentonite and Na2SO4It is put into ball mill, carries out
Batch mixing, mixing time 4h, mixed material is made；Wherein, carbon and the low-grade powder containing chromic vanadium-titanium ferroferrite in coal dust are reduced
The oxygen of middle ferriferous oxide, by carbon-to-oxygen ratio (C/O)=1.2, i.e., in mass ratio, low-grade powder containing chromic vanadium-titanium ferroferrite：Reduction coal
Powder=4.27, bentonite content are 1.5%, Na of mixed material quality2SO4Content is the 4% of total mixture material；
Step 2, pelletizing：
(1) to mixed material, water is added, mixing, boils in a covered pot over a slow fire material 30min；Wherein, in mass ratio, water is added in mixed material
Amount：Mixed material=11%；
(2) material that will have been boiled in a covered pot over a slow fire, it is put into the balling disk (-sc) that rotating speed is 19r/min, progress pelletizing, in balling process, adds water,
The low-grade pelletizing containing chromic vanadium-titanium ferroferrite that granularity is 10~13mm is made, wherein, the obtained low-grade titanium of vanadium containing chromium type magnetic
In iron ore pellets, the weight content of water is 12%；
(3) low-grade pelletizing containing chromic vanadium-titanium ferroferrite is put into baking oven 5h, dried, the pelletizing dried；
Step 3, it is calcined：
(1) the pelletizing embedment of drying is filled into the graphite crucible that particle mean size is 0.6~3mm lump coal, is put into high-temperature box type
In stove；
(2) coal base pelletizing autoreduction high-temperature calcination process is：Under nitrogen protection atmosphere, high temperature box furnace is with 8 DEG C/min
Programming rate, from room temperature to 1300 DEG C, high-temperature roasting 40min, obtain the metallized pellet of high-temperature roasting；
(3) metallized pellet of high-temperature roasting is taken out from high temperature box furnace, buries coal spontaneous and be cooled to room temperature, obtained cold
But metallized pellet, the degree of metalization for measuring the low-grade pelletizing containing chromic vanadium-titanium ferroferrite are 99.82%；
Step 4, magnetic separation separates
(1) metallized pellet of cooling is put into sealed type sample pulverizer, crushes, obtain granularity and be less than 200 purposes
Metallized pellet powder；
(2) magnetic separation separation is carried out to metallized pellet powder with the magnetic separation tube that magnetic field intensity is 160kA/m, obtained rich in iron
Magnetic Materials and the nonmagnetics rich in titanium, wherein, the composition and its mass percent that Magnetic Materials include are that TFe is 74.52%,
MFe is 70.22%, V 1.15%, Cr 0.0438%, TiO2For 11.04%, the composition and its quality that nonmagnetics includes
Percentage is that TFe is 6.07%, TiO2For 37.43%, V 0.59%, Cr is<0.0068%, the rate of recovery of wherein iron is
94.67%, vanadium has in 74.02% entrance Magnetic Materials, and chromium has 90.26% to enter in Magnetic Materials, and titanium has 74.08% entrance non magnetic
In thing.
Claims (8)
- A kind of 1. method of the low-grade magnetic separation of metallized pellet containing chromic vanadium-titanium ferroferrite separation, it is characterised in that by following step It is rapid to carry out：Step 1, batch mixing：Weigh low-grade powder containing chromic vanadium-titanium ferroferrite, reduction coal dust, binding agent and additive and carry out batch mixing, mixture is made Material；Wherein, additive B2O3、Na2CO3、CaF2、Na2SO4Or CaCO3In one kind, reduce the carbon in coal dust and low-grade contain The oxygen of ferriferous oxide in chromic vanadium-titanium ferroferrite powder, by carbon-to-oxygen ratio=1.1 ~ 1.4, binder content for mixed material quality 1 ~ 2%, additive level is the 0 ~ 8% of mixed material quality；The TFe of the described low-grade powder containing chromic vanadium-titanium ferroferrite is 43.0 ~ 45.0wt.%, comprising chemical composition and its weight Percentage is Fe3O4：40.0 ~ 42.7%, FeO：17.0 ~ 19.0%, CaO：3.0 ~ 4.0%, SiO2：6.5 ~ 7.5%, MgO：0.6~ 0.8%, Al2O3：1.5 ~ 2.1%, TiO2：20.0 ~ 22.0%, V2O5：1.6 ~ 1.8%, Cr2O3：0.02 ~ 0.2%, S≤0.05%, P≤ 0.01%, surplus is inevitable impurity；Step 2, pelletizing：(1) to mixed material, water is added, mixing, boils in a covered pot over a slow fire 30 ~ 40min of material；Wherein, in mass ratio, water is added in mixed material Amount：Mixed material=8 ~ 11%；(2) material boiled in a covered pot over a slow fire is subjected to pelletizing, in balling process, adds water, the low-grade vanadium containing chromium type that granularity is 7 ~ 16 mm is made Titanomagnetite pelletizing, wherein, in obtained low-grade pelletizing containing chromic vanadium-titanium ferroferrite, the weight content of water is 9 ~ 12%；(3) low-grade pelletizing containing chromic vanadium-titanium ferroferrite is put into oven for drying, the pelletizing dried；Step 3, it is calcined：(1) the pelletizing embedment of drying is filled into the graphite crucible of lump coal, be put into high temperature box furnace；(2) coal base pelletizing autoreduction high-temperature calcination process is：Under argon gas or nitrogen protection atmosphere, high temperature box furnace is with 8 ~ 12 DEG C/min programming rate, from room temperature to 1275 ~ 1325 DEG C, 15 ~ 45min of high-temperature roasting, obtain the metal of high-temperature roasting Pellet；(3) by the metallized pellet of high-temperature roasting, room temperature is cooled to, the metallized pellet cooled down；Step 4, magnetic separation separates(1) by the metallized pellet of cooling, crush, obtain the metallized pellet powder that granularity is less than 200 mesh, low-grade vanadium containing chromium type The degree of metalization of titanomagnetite pelletizing reaches more than 90%；(2) magnetic separation separation is carried out to metallized pellet powder with the magnetic separation tube that magnetic field intensity is 130 ~ 200kA/m, obtained rich in iron Magnetic Materials and the nonmagnetics rich in titanium.
- 2. the method for the low-grade magnetic separation of metallized pellet containing chromic vanadium-titanium ferroferrite separation as claimed in claim 1, its feature It is, in described low-grade powder containing chromic vanadium-titanium ferroferrite, the part below the mesh of granularity 200 accounts for more than the 70% of gross weight, Part below 100 mesh accounts for more than the 95% of gross weight；Described reduction coal dust, particle mean size is below 200 mesh；Described is viscous Knot agent is bentonite, and particle mean size is below 200 mesh.
- 3. the method for the low-grade magnetic separation of metallized pellet containing chromic vanadium-titanium ferroferrite separation as claimed in claim 1, its feature It is, in the step 1, experimental facilities used in batch mixing is ball mill, and mixing time is more than or equal to 4h.
- 4. the method for the low-grade magnetic separation of metallized pellet containing chromic vanadium-titanium ferroferrite separation as claimed in claim 1, its feature It is, in the step 2 (1), it is balling disk (-sc) that pelletizing, which prepares device therefor, and balling disk (-sc) rotating speed is in 17 ~ 19r/min；The step 2 (3) in, the low-grade drying time of pelletizing containing chromic vanadium-titanium ferroferrite is more than or equal to 5h.
- 5. the method for the low-grade magnetic separation of metallized pellet containing chromic vanadium-titanium ferroferrite separation as claimed in claim 1, its feature It is, in the step 3 (1), described lump coal particle mean size is 0.6 ~ 3 mm.
- 6. the method for the low-grade magnetic separation of metallized pellet containing chromic vanadium-titanium ferroferrite separation as claimed in claim 1, its feature It is, in the step 3 (3), the type of cooling is cold to bury coal spontaneous cooling, argon gas atmosphere cooling, nitrogen atmosphere cooling or water quenching But one kind in.
- 7. the method for the low-grade magnetic separation of metallized pellet containing chromic vanadium-titanium ferroferrite separation as claimed in claim 1, its feature It is, in the step 4 (2), it is TFe that Magnetic Materials, which include composition and its mass percent,：70.43 ~ 81.44%, MFe：68.16~ 75.80%, V：1.15 ~ 1.40%, Cr are 0.034 ~ 0.045%, TiO2：7.96 ~ 11.04%, nonmagnetics includes composition and its matter Amount percentage is TFe：4.75 ~ 10.24%, TiO2：37.43 ~ 42.21%, V：0.32 ~ 0.63%, Cr<0.01%.
- 8. the method for the low-grade magnetic separation of metallized pellet containing chromic vanadium-titanium ferroferrite separation as claimed in claim 1, its feature It is, in the step 4 (2), iron recovery reaches 88 ~ 98%, the part in vanadium enrichment to Magnetic Materials>74%, chromium is enriched to magnetic Part in property thing>85%, titanium is enriched to the part in nonmagnetics>68%.
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| CN106591572A (en) * | 2017-01-06 | 2017-04-26 | 中南大学 | Method for reinforcing preparation and reduction of carbon-containing pellets in iron ore |
| CN107012275A (en) * | 2017-02-28 | 2017-08-04 | 江苏省冶金设计院有限公司 | The restoring method of vanadium titano-magnetite |
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| CN107267748B (en) * | 2017-06-14 | 2018-08-28 | 东北大学 | A kind of high vanadium high-chromic vanadium-titanium ferroferrite pelletizing |
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| CN107881335A (en) * | 2017-11-19 | 2018-04-06 | 东北大学 | A kind of method that low chromium type vanadium titano-magnetite prepares pellet with addition of ilmenite |
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| CN110205487B (en) * | 2019-07-05 | 2021-07-30 | 攀钢集团攀枝花钢铁研究院有限公司 | Production method of fluorine-containing vanadium-titanium pellet ore |
| CN112899471B (en) * | 2021-01-19 | 2022-04-12 | 东北大学 | Method for preparing large-size composite vanadium-titanium pellet ore |
| CN113564385B (en) * | 2021-07-26 | 2023-01-20 | 中钢集团马鞍山矿山研究总院股份有限公司 | Method for efficiently enriching, separating and recovering chromium in chromium-containing sludge in iron and steel plant |
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