CN105907948A - Magnetic separation method for low-grade chromium-containing vanadium titanium magnetite metalized pellet - Google Patents
Magnetic separation method for low-grade chromium-containing vanadium titanium magnetite metalized pellet Download PDFInfo
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- CN105907948A CN105907948A CN201610486319.9A CN201610486319A CN105907948A CN 105907948 A CN105907948 A CN 105907948A CN 201610486319 A CN201610486319 A CN 201610486319A CN 105907948 A CN105907948 A CN 105907948A
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- grade
- pelletizing
- magnetic separation
- chromic vanadium
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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
The invention discloses a magnetic separation method for a low-grade chromium-containing vanadium titanium magnetite metalized pellet, belonging to the technical field of non-blast furnace smelting in comprehensive utilization methods of low-grade chromium-containing vanadium titanium magnetite powder. The method is carried out through the following steps of (1) mixing low-grade chromium-containing vanadium titanium magnetite powder, reduced pulverized coal, a binder and an additive by weighing; (2) preparing a pellet from the mixture, and drying; (3) carrying out coal-based pellet self-reduction high-temperature roasting on the dried pellet; (4) cooling the metalized pellet subjected to high-temperature roasting; and (5) smashing the cooled metalized pellet to obtain metalized pellet powder, and then, carrying out magnetic separation by using a magnetic separation tube to obtain an iron-enriched magnetic matter and titanium-enriched nonmagnetic matters. By using the method, the utilization ratios of strategic metal vanadium, titanium and chromium are maximized on the premise that the metallization ratio and iron recovery ratio for coal-based forced reduction of the low-grade chromium-containing vanadium titanium magnetite metalized pellet are increased.
Description
Technical field
The invention belongs to low-grade containing the non-technical field of blast furnace process in chromic vanadium-titanium ferroferrite powder method of comprehensive utilization, relate to especially
And low-grade containing chromic vanadium-titanium ferroferrite metallized pellet magnetic separation separate method.
Background technology
V-ti magnetite breeze is a kind of rich in the multiple many metals intergrowth mineral having valence group unit such as ferrum, vanadium, titanium, and using value is high.
At present comparatively ripe to common vanadium titano-magnetite research, but the research containing chromic vanadium-titanium ferroferrite is still needed to be further
Systemization, and the research containing chromic vanadium-titanium ferroferrite is concentrated mainly on high-grade containing chromic vanadium-titanium ferroferrite, and to low-grade containing chromium
The research of type vanadium titano-magnetite is the deficientest, and the work of its correlational study is needed badly and carried out further.
Recently as the fast development of China's steel industry, supply falls short of demand for domestic Iron Ore Market, and low-grade iron ore powder resource is made
For a kind of Iron Ore Powder resource having Exploitative potential, having the demand being produced utilization, economic benefit is expected to significantly, and low-grade containing chromium
Type v-ti magnetite breeze is the low-grade iron ore powder resource that one of which extraction value is high, and its rich in strategy metal chromium, vanadium,
Titanium is expected to synchronization and is efficiently utilized, and is therefore sent to great expectations.
In order to alleviate blast furnace ironmaking cost in the nervous situation increased year by year, it is new that people constantly explore and research and develop beyond blast furnace ironmaking
Technology and new technology, therefore non-blast furnace ironmaking has become the focus of a research, rather than in blast furnace process, coal-based direct reduction-magnetic separation divides
Separating process has that flow process is short, energy consumption is low, the advantage of low cost is expected to expanded employing.
In order to preferably carry out the low-grade research work containing chromic vanadium-titanium ferroferrite powder, formed low-grade containing chromic vanadium-titanium ferroferrite
The theoretical system of powder, the ironmaking work in the practice of more preferable Instructing manufacture.The present invention utilizes Ka Zuo somewhere, Liaoning the most extensive
It is low-grade containing raw material based on chromic vanadium-titanium ferroferrite powder that exploitation utilizes, and has invented a kind of low-grade containing chromic vanadium-titanium ferroferrite gold
Belong to the method that pellet magnetic separation separates.
Summary of the invention
For the low-grade resources characteristic containing chromic vanadium-titanium ferroferrite powder and its non-blast furnace ironmaking research application in terms of
Blank, the present invention provides a kind of low-grade method separated containing chromic vanadium-titanium ferroferrite metallized pellet magnetic separation, and the method is improving
On the premise of this low-grade degree of metalization containing the strengthening reduction of chromic vanadium-titanium ferroferrite pelletizing coal base, iron recovery, make simultaneously
Strategy metal vanadium, titanium, the utilization rate of chromium reach to maximize.
The low-grade method separated containing chromic vanadium-titanium ferroferrite metallized pellet magnetic separation of the present invention, sequentially includes the following steps:
Step 1, batch mixing:
Weigh and low-grade carry out batch mixing containing chromic vanadium-titanium ferroferrite powder, reduction coal dust, binding agent and additive, prepare mixed material；
Wherein, additive is B2O3、Na2CO3、CaF2、Na2SO4Or CaCO3In one, reduction coal dust in carbon and low product
Position is containing the oxygen of iron oxides in chromic vanadium-titanium ferroferrite powder, and by carbon-to-oxygen ratio (C/O)=1.1～1.4, binder content is mixed material matter
The 1～2% of amount, additive level is the 0～8% of mixed material quality；
Step 2, pelletizing:
(1) to mixed material, water, mixing, stewing material 30～40min are added；Wherein, in mass ratio, mixed material adds water
Amount: mixed material=8～11%；
(2) material boiled in a covered pot over a slow fire is carried out pelletizing, in balling process, add water, make granularity be 7～16mm low-grade containing chromium type
V-ti Bearing Magnetite Pellets, wherein, prepare is low-grade containing in chromic vanadium-titanium ferroferrite pelletizing, and the weight content of water is 9～12%；
(3) the low-grade pelletizing containing chromic vanadium-titanium ferroferrite is put into oven for drying, obtain the pelletizing dried；
Step 3, roasting:
(1) the pelletizing embedment by drying fills the graphite crucible of lump coal, puts in high temperature box furnace；
(2) coal base pelletizing autoreduction high-temperature calcination process is: under argon or nitrogen protection atmosphere, and high temperature box furnace is with 8～12 DEG C
The programming rate of/min, from room temperature to 1275～1325 DEG C, high-temperature roasting 15～45min, obtains the metallization of high-temperature roasting
Pelletizing；
(3) by the metallized pellet of high-temperature roasting, it is cooled to room temperature, obtains the metallized pellet of cooling；
Step 4, magnetic separation separates
(1) by the metallized pellet of cooling, pulverize, obtain the granularity metallized pellet powder less than 200 mesh；
(2) with the magnetic separation tube that magnetic field intensity is 130～200kA/m, metallized pellet powder is carried out magnetic separation separation, obtain rich in ferrum
Magnetic Materials and the nonmagnetics rich in titanium.
Wherein,
In described step 1, the described low-grade TFe containing chromic vanadium-titanium ferroferrite powder is 43.0～45.0wt.%, the change comprised
Study point and percentage by weight 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.
In described step 1, described is low-grade containing in chromic vanadium-titanium ferroferrite powder, and the part below granularity 200 mesh accounts for gross weight
More than 70%, the part below 100 mesh accounts for more than the 95% of gross weight.
In described step 1, described reduction coal dust, particle mean size is below 200 mesh, and the volatile content of reduction coal dust is higher,
Content of ashes is relatively low.
In described step 1, described binding agent is bentonite, and particle mean size is below 200 mesh.
In described step 1, described carbon-to-oxygen ratio computing formula is:
C/o=[mcoal×wc)/Mc]/{[mors×(wO, Fe2O3+wO, FeO)]/Mo}
Wherein, mcoal: the quality (g) of reduction coal dust, more: the low-grade quality (g) containing chromic vanadium-titanium ferroferrite powder, wc:
The fixed carbon content (%) of reduction coal dust, wO, Fe2O3: Fe2O3The percentage ratio (%) of middle oxygen, wO, FeO: the percentage ratio of oxygen in FeO
(%), Mc: the molal weight (g/mol) of carbon, Mo: the molal weight (g/mol) of oxygen.
Wherein,
In mass ratio, reduction coal dust: low-grade containing chromic vanadium-titanium ferroferrite powder=4.66～3.66.
In described step 1, experimental facilities used by batch mixing is ball mill, and mixing time is more than or equal to 4h.
In described step 2 (1), it is balling disk (-sc) that pelletizing prepares device therefor, and balling disk (-sc) rotating speed is 17～19r/min.
In described step 2 (3), low-grade containing chromic vanadium-titanium ferroferrite pelletizing drying time more than or equal to 5h.
In described step 3 (1), described lump coal particle mean size is 0.6～3mm.
In described step 3 (2), roasting process is carried out under argon or nitrogen protection atmosphere, prevents the pelletizing of reduction from reoxidizing.
Described step 3 (2), for carrying out coal base pelletizing autoreduction high-temperature calcination process to pelletizing.
In described step 3 (3), the type of cooling is for burying coal spontaneous cooling, argon gas atmosphere cooling, nitrogen atmosphere cooling or water quenching cooling
In one.
In described step 4 (1), the equipment used by pulverizing is sealed type sample pulverizer.
In described step 4 (2), Magnetic Materials comprises composition and mass percent is TFe:70.43～81.44%, MFe:
68.16～75.80%, V:1.15～1.40%, Cr is 0.034～0.045%, TiO2: 7.96～11.04%, nonmagnetics comprises into
Divide and mass percent is TFe:4.75～10.24%, TiO2: 37.43～42.21%, V:0.32～0.63%, Cr < 0.01%.
In described 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%.
The low-grade degree of metalization containing chromic vanadium-titanium ferroferrite pelletizing of the present invention reaches more than 90%.
The low-grade method separated containing chromic vanadium-titanium ferroferrite metallized pellet magnetic separation of the present invention, compared to prior art, it has
Benefit effect is: takes full advantage of low-grade containing chromic vanadium-titanium ferroferrite powder resource, greatly enhances ferrum, chromium, vanadium, titanium
Etc. there being valence group unit utilization rate；This metallized pellet magnetic separation separating technology flow process is short, simple to operate, and in technical process, coal dust replaces
Coke, reduces energy consumption, has saved cost；The additive B added2O3, Na2CO3, CaF2, Na2SO4, CaCO3
It is beneficial to promote growing up of the low-grade reduction containing chromic vanadium-titanium ferroferrite powder and iron granule, and then the separation of beneficially slag ferrum；Also
The type of cooling that sample after former roasting uses, it is possible to effectively prevent going back original sample and reoxidize, it is ensured that the gold of metallized pellet
Belonging to rate and reach between 90～99.85%, iron recovery reaches 88～98%；Magnetic separation is except the raising of beneficially iron recovery, also simultaneously
Be conducive to valence group unit vanadium, chromium and the enrichment of titanium and recycling, 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%.The present invention uses low-grade containing chromium type v-ti magnetite
Ore deposit pelletizing preparation technology, can meet enterprises production locale requirement.
Accompanying drawing explanation
Fig. 1 is the process chart of the low-grade method separated containing chromic vanadium-titanium ferroferrite metallized pellet magnetic separation of the present invention；
Fig. 2 is the ore deposit phasor of the metallized pellet that the embodiment of the present invention 3 obtains；A () amplifies 200 times；B () amplifies 5000 times；
Fig. 3 is the XRD figure spectrum of the metallized pellet that the embodiment of the present invention 3 obtains；
Fig. 4 is the XRD figure spectrum of the magnetic product that the embodiment of the present invention 3 obtains；
Fig. 5 is the XRD figure spectrum of the non magnetic product that the embodiment of the present invention 3 obtains.
Detailed description of the invention
The embodiment of the present invention low-grade containing chromic vanadium-titanium ferroferrite powder from Ka Zuo somewhere, Liaoning.
The low-grade TFe containing chromic vanadium-titanium ferroferrite powder selected in the embodiment of the present invention is 43.0～45.0wt.%, the change comprised
Study point and percentage by weight 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.
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, grain
The part spending below 200 mesh accounts for more than the 50% of gross weight, and purity is >=98%.
With embodiment, present invention process is described further below in conjunction with the accompanying drawings.
The process chart that the embodiment of the present invention uses is as shown in Figure 1.
Embodiment 1
A kind of low-grade method separated containing chromic vanadium-titanium ferroferrite metallized pellet magnetic separation, sequentially includes the following steps:
Step 1, batch mixing:
Weigh and low-grade put in ball mill containing chromic vanadium-titanium ferroferrite powder, reduction coal dust, bentonite, carry out batch mixing, during batch mixing
Between be 4h, prepare mixed material；Wherein, the carbon and low-grade containing iron oxides in chromic vanadium-titanium ferroferrite powder in reduction coal dust
Oxygen, by carbon-to-oxygen ratio (C/O)=1.2, in mass ratio, the most low-grade containing chromic vanadium-titanium ferroferrite powder: reduction coal dust=4.27, bentonite
Content is the 2% of mixed material quality；
Step 2, pelletizing:
(1) to mixed material, water, mixing, stewing material 40min are added；Wherein, in mass ratio, mixed material adds the amount of water:
Mixed material=8%；
(2) material that will have boiled in a covered pot over a slow fire, puts in the balling disk (-sc) that rotating speed is 17r/min, carries out pelletizing, in balling process, adds water, system
Become granularity be 8～12mm low-grade containing chromic vanadium-titanium ferroferrite pelletizing, wherein, prepare low-grade containing chromic vanadium-titanium ferroferrite
In pelletizing, the weight content of water is 9%；
(3) the low-grade pelletizing containing chromic vanadium-titanium ferroferrite is put into baking oven 5h, dry, obtain the pelletizing dried；
Step 3, roasting:
(1) the pelletizing embedment of drying is filled the graphite crucible that particle mean size is 0.6～3mm lump coal, put in high temperature box furnace；
(2) coal base pelletizing autoreduction high-temperature calcination process is: under argon atmosphere, and high temperature box furnace is with the intensification of 8 DEG C/min
Speed, from room temperature to 1300 DEG C, high-temperature roasting 30min, obtains the metallized pellet of high-temperature roasting；
(3) metallized pellet of high-temperature roasting is taken out from high temperature box furnace, bury coal spontaneous and be cooled to room temperature, obtain the gold of cooling
Belonging to pellet, recording the low-grade degree of metalization containing chromic vanadium-titanium ferroferrite pelletizing is 99.13%；
Step 4, magnetic separation separates
(1) metallized pellet of cooling is put in sealed type sample pulverizer, pulverize, obtain the granularity metallization less than 200 mesh
Pelletizing powder；
(2) with the magnetic separation tube that magnetic field intensity is 180kA/m, metallized pellet powder is carried out magnetic separation separation, obtain the magnetic rich in ferrum
Thing and the nonmagnetics rich in titanium, wherein, composition that Magnetic Materials comprises and mass percent thereof be TFe be 76.57%, MFe
Being 75.80%, V is 1.33%, and Cr is 0.041%, TiO2It is 10.40%, composition that nonmagnetics comprises and percent mass thereof
Ratio is 5.38% for TFe, TiO2Being 42.21%, V is 0.49%, Cr < 0.0068%, and wherein the response rate of ferrum is 88.31%,
Vanadium has in 82.85% entrance Magnetic Materials, and chromium has in 90.92% entrance Magnetic Materials, and titanium has in 70.12% entrance nonmagnetics.
Embodiment 2
A kind of low-grade method separated containing chromic vanadium-titanium ferroferrite metallized pellet magnetic separation, sequentially includes the following steps:
Step 1, batch mixing:
Weigh and low-grade put in ball mill containing chromic vanadium-titanium ferroferrite powder, reduction coal dust, bentonite, carry out batch mixing, during batch mixing
Between be 5h, prepare mixed material；Wherein, the carbon and low-grade containing iron oxides in chromic vanadium-titanium ferroferrite powder in reduction coal dust
Oxygen, by carbon-to-oxygen ratio (C/O)=1.1, in mass ratio, the most low-grade containing chromic vanadium-titanium ferroferrite powder: reduction coal dust=4.66, bentonite
Content is the 1.5% of mixed material quality；
Step 2, pelletizing:
(1) to mixed material, water, mixing, stewing material 30min are added；Wherein, in mass ratio, mixed material adds the amount of water:
Mixed material=9%；
(2) material that will have boiled in a covered pot over a slow fire, puts in the balling disk (-sc) that rotating speed is 19r/min, carries out pelletizing, in balling process, adds water, system
Become granularity be 7～10mm low-grade containing chromic vanadium-titanium ferroferrite pelletizing, wherein, prepare low-grade containing chromic vanadium-titanium ferroferrite
In pelletizing, the weight content of water is 10%；
(3) the low-grade pelletizing containing chromic vanadium-titanium ferroferrite is put into baking oven 5.5h, dry, obtain the pelletizing dried；
Step 3, roasting:
(1) the pelletizing embedment of drying is filled the graphite crucible that particle mean size is 0.6～3mm lump coal, put in high temperature box furnace；
(2) coal base pelletizing autoreduction high-temperature calcination process is: under argon atmosphere, and high temperature box furnace is with the liter of 12 DEG C/min
Temperature speed, from room temperature to 1275 DEG C, high-temperature roasting 45min, obtains the metallized pellet of high-temperature roasting；
(3) being taken out from high temperature box furnace by the metallized pellet of high-temperature roasting, argon gas atmosphere is cooled to room temperature, obtains the gold of cooling
Belonging to pellet, recording the low-grade degree of metalization containing chromic vanadium-titanium ferroferrite pelletizing is 97.11%；
Step 4, magnetic separation separates
(1) metallized pellet of cooling is put in sealed type sample pulverizer, pulverize, obtain the granularity metallization less than 200 mesh
Pelletizing powder；
(2) with the magnetic separation tube that magnetic field intensity is 130kA/m, metallized pellet powder is carried out magnetic separation separation, obtain the magnetic rich in ferrum
Thing and the nonmagnetics rich in titanium, wherein, composition that Magnetic Materials comprises and mass percent thereof be TFe be 72.11%, MFe
Being 70.23%, V is 1.20%, and Cr is 0.045%, TiO2It is 10.79%, composition that nonmagnetics comprises and percent mass thereof
Ratio is 5.98% for TFe, TiO2Being 40.22%, V is 0.61%, Cr be < 0.01%, wherein the response rate of ferrum is 91.20%,
Vanadium has in 77.72% entrance Magnetic Materials, and chromium has in 88.86% entrance Magnetic Materials, and titanium has in 68.01% entrance nonmagnetics.
Embodiment 3
A kind of low-grade method separated containing chromic vanadium-titanium ferroferrite metallized pellet magnetic separation, sequentially includes the following steps:
Step 1, batch mixing:
Weigh low-grade containing chromic vanadium-titanium ferroferrite powder, reduction coal dust, bentonite and CaF2Put in ball mill, carry out batch mixing,
Mixing time is 5h, prepares mixed material；Wherein, the carbon and low-grade containing ferrum oxygen in chromic vanadium-titanium ferroferrite powder in reduction coal dust
The oxygen of compound, by carbon-to-oxygen ratio (C/O)=1.2, in mass ratio, the most low-grade containing chromic vanadium-titanium ferroferrite powder: reduction coal dust=4.27,
Bentonite content is the 2% of mixed material quality, CaF2Content is the 8% of total mixture material；
Step 2, pelletizing:
(1) to mixed material, water, mixing, stewing material 30min are added；Wherein, in mass ratio, mixed material adds the amount of water:
Mixed material=9%；
(2) material that will have boiled in a covered pot over a slow fire, puts in the balling disk (-sc) that rotating speed is 17r/min, carries out pelletizing, in balling process, adds water, system
Become granularity be 10～13mm low-grade containing chromic vanadium-titanium ferroferrite pelletizing, wherein, prepare low-grade containing chromium type v-ti magnetite
In the pelletizing of ore deposit, the weight content of water is 9%；
(3) the low-grade pelletizing containing chromic vanadium-titanium ferroferrite is put into baking oven 5.5h, dry, obtain the pelletizing dried；
Step 3, roasting:
(1) the pelletizing embedment of drying is filled the graphite crucible that particle mean size is 0.6～3mm lump coal, put in high temperature box furnace；
(2) coal base pelletizing autoreduction high-temperature calcination process is: under argon atmosphere, and high temperature box furnace is with the liter of 10 DEG C/min
Temperature speed, from room temperature to 1300 DEG C, high-temperature roasting 30min, obtains the metallized pellet of high-temperature roasting；
(3) being taken out from high temperature box furnace by the metallized pellet of high-temperature roasting, nitrogen atmosphere is cooled to room temperature, obtains the gold of cooling
Belonging to pellet, recording the low-grade degree of metalization containing chromic vanadium-titanium ferroferrite pelletizing is 98.91%；
Step 4, magnetic separation separates
(1) metallized pellet of cooling is put in sealed type sample pulverizer, pulverize, obtain the granularity metallization less than 200 mesh
Pelletizing powder；
(2) with the magnetic separation tube that magnetic field intensity is 160kA/m, metallized pellet powder is carried out magnetic separation separation, obtain the magnetic rich in ferrum
Thing and the nonmagnetics rich in titanium, wherein, composition and mass percent thereof that Magnetic Materials comprises be: TFe is 77.36%, MFe
Being 72.88%, V is 1.40%, and Cr is 0.034%, TiO2It is 7.96%, composition that nonmagnetics comprises and mass percent thereof
For: TFe is 4.75%, TiO2Being 39.35%, V is 0.32%, Cr be < 0.0068%, wherein the response rate of ferrum is 92.10%,
Vanadium has in 83.72% entrance Magnetic Materials, and chromium has in 85.21% entrance Magnetic Materials, and titanium has in 80.79% entrance nonmagnetics.
Wherein, as in figure 2 it is shown, wherein, (a) is for amplifying 200 times for the ore deposit phasor of the metallized pellet obtained；B () is amplification 5000
Times, white portion corresponding for A in (b) is metallic iron phase, and Dark grey part corresponding for B is TiO2Phase, remaining black is mainly mutually
Stone-like pulse phase；The XRD figure of the metallized pellet obtained is composed as shown in Figure 3；The XRD figure spectrum of the magnetic product obtained is shown in Fig. 4；
The XRD figure spectrum of the non magnetic product obtained is shown in Fig. 5.
Embodiment 4
A kind of low-grade method separated containing chromic vanadium-titanium ferroferrite metallized pellet magnetic separation, sequentially includes the following steps:
Step 1, batch mixing:
Weigh low-grade containing chromic vanadium-titanium ferroferrite powder, reduction coal dust, bentonite and Na2CO3Put in ball mill, mix
Material, mixing time is 5h, prepares mixed material；Wherein, the carbon and low-grade containing in chromic vanadium-titanium ferroferrite powder in reduction coal dust
The oxygen of iron oxides, by carbon-to-oxygen ratio (C/O)=1.4, in mass ratio, the most low-grade containing chromic vanadium-titanium ferroferrite powder: reduction coal dust=3.66,
Bentonite content is the 1% of mixed material quality, Na2CO3Content is the 4% of total mixture material；
Step 2, pelletizing:
(1) to mixed material, water, mixing, stewing material 30min are added；Wherein, in mass ratio, mixed material adds the amount of water:
Mixed material=11%；
(2) material that will have boiled in a covered pot over a slow fire, puts in the balling disk (-sc) that rotating speed is 18r/min, carries out pelletizing, in balling process, adds water, system
Become granularity be 12～16mm low-grade containing chromic vanadium-titanium ferroferrite pelletizing, wherein, prepare low-grade containing chromium type v-ti magnetite
In the pelletizing of ore deposit, the weight content of water is 12%；
(3) the low-grade pelletizing containing chromic vanadium-titanium ferroferrite is put into baking oven 5h, dry, obtain the pelletizing dried；
Step 3, roasting:
(1) the pelletizing embedment of drying is filled the graphite crucible that particle mean size is 0.6～3mm lump coal, put in high temperature box furnace；
(2) coal base pelletizing autoreduction high-temperature calcination process is: under argon atmosphere, and high temperature box furnace is with the intensification of 8 DEG C/min
Speed, from room temperature to 1325 DEG C, high-temperature roasting 15min, obtains the metallized pellet of high-temperature roasting；
(3) being taken out from high temperature box furnace by the metallized pellet of high-temperature roasting, water quenching cooling, to room temperature, is then placed in baking oven,
Carrying out vacuum drying, obtain the metallized pellet of cooling, recording the low-grade degree of metalization containing chromic vanadium-titanium ferroferrite pelletizing is
98.76%；
Step 4, magnetic separation separates
(1) metallized pellet of cooling is put in sealed type sample pulverizer, pulverize, obtain the granularity metallization less than 200 mesh
Pelletizing powder；
(2) with the magnetic separation tube that magnetic field intensity is 200kA/m, metallized pellet powder is carried out magnetic separation separation, obtain the magnetic rich in ferrum
Thing and the nonmagnetics rich in titanium, wherein, composition that Magnetic Materials comprises and mass percent thereof be TFe be 81.44%, MFe
Being 74.60%, V is 1.33%, and Cr is 0.044%, TiO2It is 9.78%, composition that nonmagnetics comprises and mass percent thereof
It is 10.24% for TFe, TiO2Being 41.02%, V is 0.63%, and Cr is 0.0064%, and wherein the response rate of ferrum is 97.19%,
Vanadium has in 76.74% entrance Magnetic Materials, and chromium has in 91.46% entrance Magnetic Materials, and titanium has in 73.03% entrance nonmagnetics.
Embodiment 5
A kind of low-grade method separated containing chromic vanadium-titanium ferroferrite metallized pellet magnetic separation, sequentially includes the following steps:
Step 1, batch mixing:
Weigh low-grade containing chromic vanadium-titanium ferroferrite powder, reduction coal dust, bentonite and B2O3Put in ball mill, carry out batch mixing,
Mixing time is 5h, prepares mixed material；Wherein, the carbon and low-grade containing ferrum oxygen in chromic vanadium-titanium ferroferrite powder in reduction coal dust
The oxygen of compound, by carbon-to-oxygen ratio (C/O)=1.2, in mass ratio, the most low-grade containing chromic vanadium-titanium ferroferrite powder: reduction coal dust=4.27,
Bentonite content is the 2% of mixed material quality, B2O3Content is the 8% of total mixture material；
Step 2, pelletizing:
(1) to mixed material, water, mixing, stewing material 30min are added；Wherein, in mass ratio, mixed material adds the amount of water:
Mixed material=11%；
(2) material that will have boiled in a covered pot over a slow fire, puts in the balling disk (-sc) that rotating speed is 17r/min, carries out pelletizing, in balling process, adds water, system
Become granularity be 9～12mm low-grade containing chromic vanadium-titanium ferroferrite pelletizing, wherein, prepare low-grade containing chromic vanadium-titanium ferroferrite
In pelletizing, the weight content of water is 12%；
(3) the low-grade pelletizing containing chromic vanadium-titanium ferroferrite is put into baking oven 5h, dry, obtain the pelletizing dried；
Step 3, roasting:
(1) the pelletizing embedment of drying is filled the graphite crucible that particle mean size is 0.6～3mm lump coal, put in high temperature box furnace；
(2) coal base pelletizing autoreduction high-temperature calcination process is: under argon atmosphere, and high temperature box furnace is with the liter of 12 DEG C/min
Temperature speed, from room temperature to 1300 DEG C, high-temperature roasting 30min, obtains the metallized pellet of high-temperature roasting；
(3) metallized pellet of high-temperature roasting is taken out from high temperature box furnace, bury coal spontaneous and be cooled to room temperature, obtain the gold of cooling
Belonging to pellet, recording the low-grade degree of metalization containing chromic vanadium-titanium ferroferrite pelletizing is 99.34%；
Step 4, magnetic separation separates
(1) metallized pellet of cooling is put in sealed type sample pulverizer, pulverize, obtain the granularity metallization less than 200 mesh
Pelletizing powder；
(2) with the magnetic separation tube that magnetic field intensity is 160kA/m, metallized pellet powder is carried out magnetic separation separation, obtain the magnetic rich in ferrum
Thing and the nonmagnetics rich in titanium, wherein, composition that Magnetic Materials comprises and mass percent thereof be TFe be 70.43%, MFe
Being 68.16%, V is 1.23%, and Cr is 0.044%, TiO2It is 10.59%, composition that nonmagnetics comprises and percent mass thereof
Ratio is 6.92% for TFe, TiO2Being 41.82%, V is 0.49%, Cr be < 0.0068%, wherein the response rate of ferrum is 95.94%,
Vanadium has in 83.80% entrance Magnetic Materials, and chromium has in 92.85% entrance Magnetic Materials, and titanium has in 68.01% entrance nonmagnetics.
Embodiment 6
A kind of low-grade method separated containing chromic vanadium-titanium ferroferrite metallized pellet magnetic separation, sequentially includes the following steps:
Step 1, batch mixing:
Weigh low-grade containing chromic vanadium-titanium ferroferrite powder, reduction coal dust, bentonite and Na2SO4Put in ball mill, mix
Material, mixing time is 4h, prepares mixed material；Wherein, the carbon and low-grade containing in chromic vanadium-titanium ferroferrite powder in reduction coal dust
The oxygen of iron oxides, by carbon-to-oxygen ratio (C/O)=1.2, in mass ratio, the most low-grade containing chromic vanadium-titanium ferroferrite powder: reduction coal dust=4.27,
Bentonite content is the 1.5% of mixed material quality, Na2SO4Content is the 4% of total mixture material；
Step 2, pelletizing:
(1) to mixed material, water, mixing, stewing material 30min are added；Wherein, in mass ratio, mixed material adds the amount of water:
Mixed material=11%；
(2) material that will have boiled in a covered pot over a slow fire, puts in the balling disk (-sc) that rotating speed is 19r/min, carries out pelletizing, in balling process, adds water, system
Become granularity be 10～13mm low-grade containing chromic vanadium-titanium ferroferrite pelletizing, wherein, prepare low-grade containing chromium type v-ti magnetite
In the pelletizing of ore deposit, the weight content of water is 12%；
(3) the low-grade pelletizing containing chromic vanadium-titanium ferroferrite is put into baking oven 5h, dry, obtain the pelletizing dried；
Step 3, roasting:
(1) the pelletizing embedment of drying is filled the graphite crucible that particle mean size is 0.6～3mm lump coal, put in high temperature box furnace；
(2) coal base pelletizing autoreduction high-temperature calcination process is: under nitrogen protection atmosphere, and high temperature box furnace is with the intensification of 8 DEG C/min
Speed, from room temperature to 1300 DEG C, high-temperature roasting 40min, obtains the metallized pellet of high-temperature roasting；
(3) metallized pellet of high-temperature roasting is taken out from high temperature box furnace, bury coal spontaneous and be cooled to room temperature, obtain the gold of cooling
Belonging to pellet, recording the low-grade degree of metalization containing chromic vanadium-titanium ferroferrite pelletizing is 99.82%；
Step 4, magnetic separation separates
(1) metallized pellet of cooling is put in sealed type sample pulverizer, pulverize, obtain the granularity metallization less than 200 mesh
Pelletizing powder；
(2) with the magnetic separation tube that magnetic field intensity is 160kA/m, metallized pellet powder is carried out magnetic separation separation, obtain the magnetic rich in ferrum
Thing and the nonmagnetics rich in titanium, wherein, composition that Magnetic Materials comprises and mass percent thereof be TFe be 74.52%, MFe
Being 70.22%, V is 1.15%, and Cr is 0.0438%, TiO2It is 11.04%, composition that nonmagnetics comprises and percent mass thereof
Ratio is 6.07% for TFe, TiO2Being 37.43%, V is 0.59%, Cr be < 0.0068%, wherein the response rate of ferrum is 94.67%,
Vanadium has in 74.02% entrance Magnetic Materials, and chromium has in 90.26% entrance Magnetic Materials, and titanium has in 74.08% entrance nonmagnetics.
Claims (10)
1. the low-grade method separated containing chromic vanadium-titanium ferroferrite metallized pellet magnetic separation, it is characterised in that according to the following steps
Carry out:
Step 1, batch mixing:
Weigh and low-grade carry out batch mixing containing chromic vanadium-titanium ferroferrite powder, reduction coal dust, binding agent and additive, prepare mixed material；
Wherein, additive is B2O3、Na2CO3、CaF2、Na2SO4Or CaCO3In one, reduction coal dust in carbon and low product
Position is containing the oxygen of iron oxides in chromic vanadium-titanium ferroferrite powder, and by carbon-to-oxygen ratio=1.1～1.4, binder content is mixed material quality
1～2%, additive level is the 0～8% of mixed material quality；
Step 2, pelletizing:
(1) to mixed material, water, mixing, stewing material 30～40min are added；Wherein, in mass ratio, mixed material adds water
Amount: mixed material=8～11%；
(2) material boiled in a covered pot over a slow fire is carried out pelletizing, in balling process, add water, make granularity be 7～16mm low-grade containing chromium type
V-ti Bearing Magnetite Pellets, wherein, prepare is low-grade containing in chromic vanadium-titanium ferroferrite pelletizing, and the weight content of water is 9～12%；
(3) the low-grade pelletizing containing chromic vanadium-titanium ferroferrite is put into oven for drying, obtain the pelletizing dried；
Step 3, roasting:
(1) the pelletizing embedment by drying fills the graphite crucible of lump coal, puts in high temperature box furnace；
(2) coal base pelletizing autoreduction high-temperature calcination process is: under argon or nitrogen protection atmosphere, and high temperature box furnace is with 8～12 DEG C
The programming rate of/min, from room temperature to 1275～1325 DEG C, high-temperature roasting 15～45min, obtains the metallization of high-temperature roasting
Pelletizing；
(3) by the metallized pellet of high-temperature roasting, it is cooled to room temperature, obtains the metallized pellet of cooling；
Step 4, magnetic separation separates
(1) by the metallized pellet of cooling, pulverize, obtain the granularity metallized pellet powder less than 200 mesh；
(2) with the magnetic separation tube that magnetic field intensity is 130～200kA/m, metallized pellet powder is carried out magnetic separation separation, obtain rich in ferrum
Magnetic Materials and the nonmagnetics rich in titanium.
The most low-grade method separated containing chromic vanadium-titanium ferroferrite metallized pellet magnetic separation, its feature exists
In, the described low-grade TFe containing chromic vanadium-titanium ferroferrite powder is 43.0～45.0wt.%, the chemical composition comprised and weight hundred thereof
Proportion by subtraction 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.
The most low-grade method separated containing chromic vanadium-titanium ferroferrite metallized pellet magnetic separation, its feature exists
In, described low-grade containing in chromic vanadium-titanium ferroferrite powder, the part below granularity 200 mesh accounts for more than the 70% of gross weight, and 100
Part below mesh accounts for more than the 95% of gross weight；Described reduction coal dust, particle mean size is below 200 mesh；Described bonding
Agent is bentonite, and particle mean size is below 200 mesh.
The most low-grade method separated containing chromic vanadium-titanium ferroferrite metallized pellet magnetic separation, its feature exists
In, in described step 1, experimental facilities used by batch mixing is ball mill, and mixing time is more than or equal to 4h.
The most low-grade method separated containing chromic vanadium-titanium ferroferrite metallized pellet magnetic separation, its feature exists
In, in described step 2 (1), it is balling disk (-sc) that pelletizing prepares device therefor, and balling disk (-sc) rotating speed is 17～19r/min；Described step 2 (3)
In, low-grade containing chromic vanadium-titanium ferroferrite pelletizing drying time more than or equal to 5h.
The most low-grade method separated containing chromic vanadium-titanium ferroferrite metallized pellet magnetic separation, its feature exists
In, in described step 3 (1), described lump coal particle mean size is 0.6～3mm.
The most low-grade method separated containing chromic vanadium-titanium ferroferrite metallized pellet magnetic separation, its feature exists
In, in described step 3 (3), the type of cooling is for burying coal spontaneous cooling, argon gas atmosphere cooling, nitrogen atmosphere cooling or water quenching cooling
In one.
The most low-grade method separated containing chromic vanadium-titanium ferroferrite metallized pellet magnetic separation, its feature exists
In, in described step 4 (2), Magnetic Materials comprises composition and mass percent is TFe:70.43～81.44%, MFe:
68.16～75.80%, V:1.15～1.40%, Cr is 0.034～0.045%, TiO2: 7.96～11.04%, nonmagnetics comprises into
Divide and mass percent is TFe:4.75～10.24%, TiO2: 37.43～42.21%, V:0.32～0.63%, Cr ＜ 0.01%.
The most low-grade method separated containing chromic vanadium-titanium ferroferrite metallized pellet magnetic separation, its feature exists
In, the low-grade degree of metalization containing chromic vanadium-titanium ferroferrite pelletizing reaches more than 90%.
The most low-grade method separated containing chromic vanadium-titanium ferroferrite metallized pellet magnetic separation, its feature exists
In, in described step 4 (2), iron recovery reaches 88～98%, and part ＞ 74% in vanadium enrichment to Magnetic Materials, chromium is enriched to magnetic
Part ＞ 85% in property thing, part ＞ 68% that titanium is enriched in nonmagnetics.
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