Summary of the invention
The objective of the invention is to adopt the straight line moving-bed to carry out prereduction, in the prereduction process, feed coal gas or Sweet natural gas, in the modified version shaft furnace, melt branch preparation vanadium iron intermetallic compound then and discharge titanium slag.
A kind of method that adopts the molten division technique of straight line moving-bed prereduction-shaft furnace to prepare vanadium iron intermetallic compound and titanium slag of the present invention is characterized in that including the following step:
Step 1: system batch mixing
Vanadium ferrotianium mixing ore deposit, binding agent, reductive agent and hydromining with mixing in the mechanical stirring ball mill 30 minutes~60 minutes, are obtained mixture charge;
Consumption: add 50 kilograms~100 kilograms in 3 kilograms~5 kilograms of binding agents, 100 kilograms~150 kilograms of reductive agents and water in 1000 kilograms the vanadium ferrotianium mixing ore deposit;
Binding agent is Polyanionic Cellulose (PAC), sodium lignosulfonate, sodium humate, carboxymethyl cellulose;
Reductive agent is hard coal, refinery coke, charcoal;
Step 2: system ball
Mixture charge is pressed into diameter on the pelletizing shaper be that 4 centimetres, thickness are 3 centimetres pelletizing, and pressure is 30MPa~60MPa;
Adopt electrically heated drying cabinet that pelletizing is carried out drying and dehydrating, the pelletizing water content drops to below 1%, makes dry pelletizing; Drying temperature is 120 ℃~150 ℃, and the time is 1 hour~3 hours;
Step 3: prereduction metallized pellet
Dry pelletizing is placed on the two-way linear moving-bed of plane, and be blown into coal gas and in moving process, carry out prereduction 40min~80min, make the pelletizing after the reduction;
Moving the chassis of the dry pelletizings of a plurality of splendid attires on the two-way linear moving-bed of plane, chassis has the furnace wall on four sides, helps the charging and the discharging of pelletizing, process furnace length L=4 meter, chassis travelling speed 0.1m/min~0.2m/min; The temperature of preheating zone is set to 600 ℃~1250 ℃, and the temperature of reduction zone is set to 1250 ℃~1450 ℃, and the temperature of cooling zone is set to 600 ℃~1200 ℃;
Step 4: molten vanadium iron intermetallic compound and the titanium slag of dividing of shaft furnace
Metallized pellet after the reduction is transfused in the modified version shaft furnace in the transportation of high temperature conveyer, under 1500 ℃~1650 ℃ conditions, obtains fusion vanadium iron intermetallic compound and titanium slag;
The modified version shaft furnace is to have increased spray gun, induced draft fan, double-edged fine-toothed comb on existing shaft furnace; Double-edged fine-toothed comb is divided into the body of heater of shaft furnace molten subregion and contains two parts of iron furnace cylinder, on the fuel condition that coal gas spray gun and pulverized coal gun provide, make the reduction that enters continuously after pelletizing separated by melting; Be present in the molten iron of fusing because titanium and vanadium are the forms with oxide compound, contain in the iron furnace cylinder so flow into through double-edged fine-toothed comb, after discharge port is discharged shaft furnace, and the main component of being left on the double-edged fine-toothed comb to be the slag charge of titanium slag will discharge from cinder notch; The coal gas that the coal dust that one of them spray gun sprays into sprays at another spray gun has also carried out reduction once more to reducing the back pelletizing in combustion processes; While also forms the molten district of circling round that divides before the shaft furnace air port, pulverized coal friring in the stove, and for metallized pellet drastic reduction in the shaft furnace and molten the branch provide heat, double-edged fine-toothed comb is following to be liquid vanadium-containing molten iron;
Spray gun is used for realizing supplying material continuously in stove, and this material can be fuel, auxiliary material, auxiliary agent etc.;
Induced draft fan is used for realizing that the gas with reaction process produces discharges out of the furnace;
Double-edged fine-toothed comb is used for realizing molten minute thing under the molten state bled and contains the iron furnace cylinder, and will be above double-edged fine-toothed comb without the titanium slag of fusing;
Reduction back pelletizing enters molten subregion in the modified version shaft furnace continuously through opening for feed, coal gas and colliery powder that the while lance ejection goes out burn at molten subregion, pellets will after the heat that burning produces enough allows and reduces is separated titanium, the vanadium of molten iron, vanadium water and the oxide form existence of simple substance.
Preparation method's of the present invention advantage:
1. on the two-way linear moving-bed of plane, pass through control reduction temperature and catalyst levels, the oxide compound that can realize iron reduces to greatest extent, and titanium and vanadium all are present in the slag with the oxide compound state, lay the foundation for back step melting and reducing operation cuts down the consumption of energy, plane two-way linear moving-bed characteristics are productivity height.
2. realize that with shaft furnace slag iron separates, wherein the oxide compound of vanadium obtains reduction and enters molten iron, owing to be thermopositive reaction, production cost is low, and vanadium iron metallic compound and titanium slag obtain good separation, and the productive rate of vanadium iron metallic compound is 40%~50%.
3. plane two-way linear moving-bed-shaft furnace process production efficiency height, energy consumption is low, degree of metalization is high, metal recovery rate is high.Production method of the present invention reclaims the vanadium iron intermetallic compound from ore deposit, vanadium ferrotianium mixing ore deposit the rate of recovery reaches 90%.Vanadium ferrotianium separating technology of the present invention, non-environmental-pollution is easy to industrialization promotion, social benefit and remarkable in economical benefits.
Embodiment
The present invention is described in further detail below in conjunction with drawings and Examples.
Referring to shown in Figure 1, the present invention is a kind of production technique that adopts the molten point-score of straight line moving-bed prereduction-shaft furnace to prepare vanadium iron intermetallic compound and titanium slag, and its technology includes following production stage:
Step 1: system batch mixing
Vanadium ferrotianium mixing ore deposit, binding agent, reductive agent and water (can be tap water, limpid mountain spring water etc.) be adopted in the mechanical stirring ball mill and mixed 30 minutes~60 minutes, obtain mixture charge;
Consumption: add 50 kilograms~100 kilograms in 3 kilograms~5 kilograms of binding agents, 100 kilograms~150 kilograms of reductive agents and water in 1000 kilograms the vanadium ferrotianium mixing ore deposit.
In the present invention, binding agent is Polyanionic Cellulose (PAC), sodium lignosulfonate, sodium humate, carboxymethyl cellulose;
Described Polyanionic Cellulose PAC, content are 99%, and main component is a hydrocarbon polymer, and other impurity trace are not chloride, appearance white or micro-yellow powder and particle.230 ℃ of carbonization temperatures, 375 ℃ of temperature of combustion.Combustion products is carbonic acid gas and water, and burning does not produce the material of Dioxins.
In the present invention, reductive agent is hard coal, refinery coke, charcoal;
Described anthracitic ash oontent 8%, volatile content 9.5%, fixed carbon content 82.5%, particle diameter are 0.1mm~1mm.
Described refinery coke fixed carbon content 94%, particle diameter is 0.1mm~1mm.
Described charcoal fixed carbon content 96%, particle diameter is 0.5mm~1mm.
Step 2: system ball
Mixture charge is pressed into diameter on the pelletizing shaper be that 4 centimetres, thickness are 3 centimetres pelletizing, and pressure is 30MPa~60MPa; The pelletizing dropping strength: 0.7 meter secondary does not break; Pelletizing mean compressive strength: 1304.77 Ns/(measuring 60 pelletizings altogether);
Adopt electrically heated drying cabinet that pelletizing is carried out drying and dehydrating, the pelletizing water content drops to below 1%, makes dry pelletizing; Drying temperature is 120 ℃~150 ℃, and the time is 1 hour~3 hours;
In the present invention, dry pelletizing dropping strength: 5 meters once do not break; Hot strength: 1000 ℃ of not efflorescence.
Step 3: prereduction metallized pellet
Dry pelletizing is placed on the two-way linear moving-bed of plane, and be blown into coal gas and in moving process, carry out prereduction 40min~80min, make the pelletizing after the reduction;
In the present invention, moving the chassis of the dry pelletizing of a plurality of splendid attires on the two-way linear moving-bed of plane, chassis has the furnace wall on four sides, helps the charging and the discharging of pelletizing.General process furnace length L=4 meters, chassis travelling speed 0.1m/min~0.2m/min.In the length L scope of plane two-way linear moving-bed, be provided with and land bonnet and screw rod burner, and bed is divided into three districts (as shown in Figure 2), i.e. preheating zone, reduction zone and cooling zone on travel direction.The temperature of preheating zone is set to 600 ℃~1250 ℃ in the present invention, and the temperature of reduction zone is set to 1250 ℃~1450 ℃, and the temperature of cooling zone is set to 600 ℃~1200 ℃.
In the present invention, be blown into that coal gas is combustion-supporting can to make the iron in the metallized pellet be reduced, exist with the fe form; And titanium and vanadium still exist with the form of oxide compound.
In the present invention, plane two-way linear moving-bed dry pelletizing is carried out separating treatment, and the flow of coal gas is not done requirement under the heat energy condition that the coal gas that is burning provides, and only needs to guarantee that dry pelletizing is getting final product of burning in preheating zone and reduction zone coal gas.Adopt plane two-way linear moving-bed to carry out reductive and handle, saved the production time than molten minute stove of routine, and helped industrialized production.On the other hand, separate for real product the condition that provides necessary with, make the rate of recovery of product improve.
Step 4: molten vanadium iron intermetallic compound and the titanium slag of dividing of shaft furnace
Metallized pellet after the reduction is transfused in the modified version shaft furnace (shown in Fig. 2 A) in the transportation of high temperature conveyer, under 1500 ℃~1650 ℃ conditions, obtains fusion vanadium iron intermetallic compound and titanium slag.
Referring to the modified version shaft furnace shown in Fig. 2 A, this modified version shaft furnace is to have increased spray gun, induced draft fan, double-edged fine-toothed comb etc. on existing shaft furnace; Double-edged fine-toothed comb is divided into the body of heater of shaft furnace molten subregion and contains two parts of iron furnace cylinder, on the fuel condition that coal gas spray gun and pulverized coal gun provide, make the reduction that enters continuously after pelletizing separated by melting.Be present in the molten iron of fusing because titanium and vanadium are the forms with oxide compound, contain in the iron furnace cylinder so flow into through double-edged fine-toothed comb, after discharge port is discharged shaft furnace, and the main component of being left on the double-edged fine-toothed comb to be the slag charge of titanium slag will discharge from cinder notch.The coal gas that the coal dust that one of them spray gun sprays into sprays at another spray gun has also carried out reduction once more to reducing the back pelletizing in combustion processes; While also forms the molten district of circling round that divides before the shaft furnace air port, pulverized coal friring in the stove, and for metallized pellet drastic reduction in the shaft furnace and molten the branch provide heat, double-edged fine-toothed comb is following to be liquid vanadium-containing molten iron.
Spray gun is used for realizing supplying material continuously in stove, and this material can be fuel, auxiliary material, auxiliary agent etc.
Induced draft fan is used for realizing that the gas with reaction process produces discharges out of the furnace.
Double-edged fine-toothed comb is used for realizing molten minute thing under the molten state bled and contains the iron furnace cylinder, and will be above double-edged fine-toothed comb without the titanium slag of fusing.
Reduction back pelletizing enters molten subregion in the modified version shaft furnace continuously through opening for feed, coal gas and colliery powder that the while lance ejection goes out burn at molten subregion, pellets will after the heat that burning produces enough allows and reduces is separated titanium, the vanadium of molten iron, vanadium water and the oxide form existence of simple substance.
In the present invention, the modified version shaft furnace is the drastic reduction reactor, and metallized pellet can be supplied with continuously, and the heat of molten branch usefulness is supplied with continuously by spray gun, has fully realized the possibility of industrialization continuous production vanadium iron intermetallic oxide compound.
In the present invention, the vanadium-containing molten iron that makes can directly or be handled the back through desulfurization and use for steel-making.
Embodiment 1
Step 1: system batch mixing
With mixing 60 minutes in vanadium ferrotianium mixing ore deposit, Polyanionic Cellulose PAC (binding agent), hard coal (reductive agent) and the tap water employing mechanical stirring ball mill (ZJM-20 periodic mechanical stirring ball mill), obtain mixture charge;
Consumption: add 100 kilograms in 5 kilograms of binding agents, 100 kilograms of reductive agents and water in 1000 kilograms the vanadium ferrotianium mixing ore deposit.
In the present invention, the composition in vanadium ferrotianium mixing ore deposit is (mass percent): full iron (TFe) 50.28%, titanium dioxide (TiO
2) 20.64%, Vanadium Pentoxide in FLAKES (V
2O
5) 0.42%, SiO
22.2%, MgO2.58%, CaO0.61%.Referring to XRD analysis figure shown in Figure 3.
Step 2: system ball
Mixture charge is pressed into pelletizing (diameter is 4 centimetres, and thickness is 3 centimetres) on pelletizing shaper (unit type QT300), pressure is 50MPa; The pelletizing dropping strength: 0.7 meter secondary does not break; Pelletizing mean compressive strength: 1304.77 Ns/(measuring 60 pelletizings altogether);
Adopt electrically heated drying cabinet that pelletizing is carried out drying and dehydrating, the pelletizing water content drops to below 1%, makes dry pelletizing; Drying temperature is 150 ℃, and the time is 2 hours;
In the present invention, dry pelletizing dropping strength: 5 meters once do not break; Hot strength: 1000 ℃ of not efflorescence.
Step 3: prereduction metallized pellet
Dry pelletizing is placed on the plane two-way linear moving-bed (unit type PSH4), and be blown into coal gas and in moving process, carry out prereduction 60min, make the pelletizing after the reduction;
In the present invention, the temperature of the preheating zone of plane two-way linear moving-bed is set to 1150 ℃, and the temperature of reduction zone is set to 1450 ℃, and the temperature of cooling zone is set to 800 ℃.
Iron in the metallized pellet is reduced, and exists with the fe form; And titanium and vanadium still exist with the form of oxide compound.
In the present invention, the dry pelletizing that step 2 is made carries out various sample numbering, i.e. No. 1 sample, No. 2 samples, No. 3 samples.Respectively to these three treatment of different temperature that sample carries out prereduction.
Quality under table 1 condition of different temperatures after molten the branch
As can be seen from Table 1, temperature raises favourable to dry pelletizing reduction.When temperature during at 1350 ℃ the rate of recovery of iron be 79%, and the rate of recovery of iron reaches 95% in the time of 1450 ℃, magnetic material content is also minimum in the slag, promptly iron-based originally is removed.Usually under high temperature like this, the oxide compound reduction rate of the iron in the iron ore is very fast, and is also very abundant, and therefore, reduction is not the limiting factor that influences iron recovery.But when temperature raises, the easier fusing of iron and slag, and the viscosity of slag reduces, mobile better, iron crystal grain also can fully be grown up in the slag, assembles and forms 3~8 millimeters abrasive grit.
1400 ℃ of following coal blending amounts of table 2 temperature mass balance that slag iron is molten simultaneously before and after dividing
Carbon in the pelletizing mainly plays the reductive agent of two effects (a) as ferriferous oxide; (b) after iron is reduced, excessive carbon is penetrated into the beginning temperature of fusion that reduces iron in the iron and makes the iron fusing.
If but carbon is superfluous too many, be scattered in the particularly cohesion of iron of gathering that carbon granule in the pelletizing will stop slag iron.Thereby cause difficulty for the separation of slag iron.When mixed carbon comtent is 8%, the rate of recovery of iron is the highest, separation influence to slag iron in 8~12% scopes is little, and when mixed carbon comtent reaches 14%, the rate of recovery of iron obviously reduces, and iron almost becomes the fine particle embedding to be distributed in the slag, and slag iron is difficult to separate, therefore, suitable mixed carbon comtent should be between 8~12%.
When the coal blending amount is 10%, and the piece iron that obtains when being 1400 ℃ of temperature, slag iron separate easily.Reasonably the molten branch condition of reduction is: content of binder is 0.3~0.5%; The coal blending amount is 8~12%; The molten branch temperature of reduction is 1400~1450 ℃.
Step 4: molten vanadium iron intermetallic compound and the titanium slag of dividing of shaft furnace
Metallized pellet after the reduction is transfused in the shaft furnace (shown in Fig. 2 A) in the transportation of high temperature conveyer, under 1500 ℃ of conditions, obtains fusion vanadium iron intermetallic compound and titanium slag.
The vanadium iron intermetallic compound that makes is carried out XRD analysis, as shown in Figure 4.The vanadium iron intermetallic compound that makes is carried out energy spectrum analysis, and shown in Fig. 4 A, the chemical ingredients of the vanadium iron metallization alloy that makes sees Table 3.
The EDAX results of table 3 vanadium iron metallization alloy
The titanium slag that makes is carried out XRD analysis, as shown in Figure 5.The titanium slag that makes is carried out energy spectrum analysis, and shown in Fig. 5 A, the chemical ingredients of isolated titanium slag sees Table 4.
The EDAX results of table 4 titanium slag
The productive rate of the vanadium iron metallic compound that the method for employing embodiment 1 makes is that 50%, 1000 kilogram of vanadium ferrotianium mixing ore deposit can access 500 kilograms of vanadium iron metallic compounds.All the other all are titanium slag.
Embodiment 2
Step 1: system batch mixing
With mixing 30 minutes in vanadium ferrotianium mixing ore deposit, carboxymethyl cellulose (binding agent), charcoal (reductive agent) and the tap water employing mechanical stirring ball mill, obtain mixture charge; Described charcoal fixed carbon content 96%, particle diameter is 1mm.
Consumption: add 100 kilograms in 3 kilograms of binding agents, 150 kilograms of reductive agents and water in 1000 kilograms the vanadium ferrotianium mixing ore deposit.
In the present invention, the composition in vanadium ferrotianium mixing ore deposit is (mass percent): full iron (TFe) 50.28%, titanium dioxide (TiO
2) 20.64%, Vanadium Pentoxide in FLAKES (V
2O
5) 0.42%, SiO
22.2%, MgO2.58%, CaO0.61%.Referring to XRD analysis figure shown in Figure 3.
Step 2: system ball
Mixture charge is pressed into diameter on the pelletizing shaper be that 4 centimetres, thickness are 3 centimetres pelletizing, and pressure is 30MPa; The pelletizing dropping strength: 0.7 meter secondary does not break; Pelletizing mean compressive strength: 1304.77 Ns/(measuring 60 pelletizings altogether);
Adopt electrically heated drying cabinet that pelletizing is carried out drying and dehydrating, the pelletizing water content drops to below 1%, makes dry pelletizing; Drying temperature is 120 ℃, and the time is 3 hours;
In the present invention, dry pelletizing dropping strength: 5 meters once do not break; Hot strength: 1000 ℃ of not efflorescence.
Step 3: prereduction metallized pellet
Dry pelletizing is placed on the two-way linear moving-bed of plane, and be blown into coal gas and in moving process, carry out prereduction 80min, make the pelletizing after the reduction; The temperature of preheating zone is set to 600 ℃ in the two-way linear moving-bed of plane, and the temperature of reduction zone is set to 1250 ℃, and the temperature of cooling zone is set to 1200 ℃.
Step 4: molten vanadium iron intermetallic compound and the titanium slag of dividing of shaft furnace
Metallized pellet after the reduction is transfused in the shaft furnace (shown in Fig. 2 A) in the transportation of high temperature conveyer, under 1600 ℃ of conditions, obtains fusion vanadium iron intermetallic compound and titanium slag.
The productive rate of the vanadium iron metallic compound that the method for employing embodiment 2 makes is that 45%, 1000 kilogram of vanadium ferrotianium mixing ore deposit can access 450 kilograms of vanadium iron metallic compounds.All the other all are titanium slag.
Embodiment 3
Step 1: system batch mixing
Vanadium ferrotianium mixing ore deposit, sodium humate (binding agent), refinery coke (reductive agent) and limpid mountain spring water adopted in the mechanical stirring ball mill mixed 40 minutes, obtain mixture charge;
Consumption: add 50 kilograms in 4 kilograms of binding agents, reductive agent 120 kg and water in 1000 kilograms the vanadium ferrotianium mixing ore deposit.
In the present invention, the composition in vanadium ferrotianium mixing ore deposit is (mass percent): full iron (TFe) 50.28%, titanium dioxide (TiO
2) 20.64%, Vanadium Pentoxide in FLAKES (V
2O
5) 0.42%, SiO
22.2%, MgO2.58%, CaO0.61%.Referring to XRD analysis figure shown in Figure 3.
Step 2: system ball
Mixture charge is pressed into diameter on the pelletizing shaper be that 4 centimetres, thickness are 3 centimetres pelletizing, and pressure is 60MPa; The pelletizing dropping strength: 0.7 meter secondary does not break; Pelletizing mean compressive strength: 1304.77 Ns/(measuring 60 pelletizings altogether);
Adopt electrically heated drying cabinet that pelletizing is carried out drying and dehydrating, the pelletizing water content drops to below 1%, makes dry pelletizing; Drying temperature is 150 ℃, and the time is 1 hour;
In the present invention, dry pelletizing dropping strength: 5 meters once do not break; Hot strength: 1000 ℃ of not efflorescence.
Step 3: prereduction metallized pellet
Dry pelletizing is placed on the two-way linear moving-bed of plane, and be blown into coal gas and in moving process, carry out prereduction 40min, make the pelletizing after the reduction; The temperature of the preheating zone of plane two-way linear moving-bed is set to 800 ℃, and the temperature of reduction zone is set to 1200 ℃, and the temperature of cooling zone is set to 600 ℃.
Iron in the metallized pellet is reduced, and exists with the fe form; And titanium and vanadium still exist with the form of oxide compound.
Step 4: molten vanadium iron intermetallic compound and the titanium slag of dividing of shaft furnace
Metallized pellet after the reduction is transfused in the shaft furnace (shown in Fig. 2 A) in the transportation of high temperature conveyer, under 1650 ℃ of conditions, obtains fusion vanadium iron intermetallic compound and titanium slag.
The productive rate of the vanadium iron metallic compound that the method for employing embodiment 3 makes is that 47%, 1000 kilogram of vanadium ferrotianium mixing ore deposit can access 470 kilograms of vanadium iron metallic compounds.All the other all are titanium slag.