CN100390070C - Method of producing synthetic rutile utilizing high-titanium slag - Google Patents
Method of producing synthetic rutile utilizing high-titanium slag Download PDFInfo
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- CN100390070C CN100390070C CNB2006100472120A CN200610047212A CN100390070C CN 100390070 C CN100390070 C CN 100390070C CN B2006100472120 A CNB2006100472120 A CN B2006100472120A CN 200610047212 A CN200610047212 A CN 200610047212A CN 100390070 C CN100390070 C CN 100390070C
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Abstract
The invention discloses a manufacturing method of artificial rutile through high-titanium slag, which comprises the following steps: heating to fuse titanium slag in the slag container; adding addictive in the slag tank; blowing oxidized gas in the slag; making titanium component enriched in the rutile selectively; controlling the cooling velocity to cool slag to indoor temperature; growing rutile phase selectively; grinding the cooled condensed slag; fining; adopting wet metallurgical separating method or ore dressing separating method to separate rutile from condensed slag; obtaining artificial rutile with high-grade TiO2.
Description
Technical field
The present invention relates to a kind of method of producing artificial rutile, particularly a kind of method of utilizing high-titanium slag to produce artificial rutile.
Background technology
At present, as the raw material of " high-grade chloride process titanium dioxide ", in short supply especially as natural rutile, artificial rutile etc. in the titanium white raw materials market of home and abroad, titanium slag has become the main raw material that chlorination process is produced titanium white.The titanium slag of the hot stove reduction method preparation in existing ore deposit contains 60～75% TiO approximately
2, grade is low, is not suitable for doing the raw material of " high-grade chloride process titanium dioxide ".Therefore, improve the titanium slag grade, meet the need of market, imperative.Anosovite is main titaniferous thing phase in the titanium slag, its TiO
2Content higher (60%-80%) be early stage crystallization product, but anosovite is crisp, and hardness is low, is unsuitable for physical sepn.Some scientific workers study around " enrichment of titanium slag " both at home and abroad in recent years, making certain gains aspect the preparation artificial rutile, now are summarized as follows.
The patent No. is the grade that 4038363 United States Patent (USP) " Upgrading sorelalag for production ofsynthetic rutile " discloses your slag (titanium slag) of raising Soret, the method for preparing artificial rutile, it be with the titanium slag after the oxidizing roasting through wet-milling, washing, twice dipping of dilute sulphuric acid, filtration, washing, 850～950 ℃ down calcining obtain the high artificial rutile of grade of titanium dioxide.
The patent No. is that 4933153 United States Patent (USP) " Method of preparing a synthetic rutile froma titaniferous slag containing magnesium values " discloses the method that titanium slag that a kind of usefulness contains magnesium prepares rutile, it is that the titanium slag after the chloridized is handled with acid or alkali steeping, remove remaining impurity, macerate obtains the high artificial rutile of grade of titanium dioxide through washing and drying.
The patent No. is that 5830420 United States Patent (USP) " Method to upgrade titania slag andresulting product " discloses the method that improves the titanium slag grade, it is that the titanium slag after oxidizing roasting and the reducing roasting is used the mineral acid acidleach being not less than under 125 ℃, 0.3445MPa～0.4823MPa, the acidleach product is after washing, alkali soak, at 600 ℃～800 ℃ titanium slags that obtain higher-grade titanium dioxide.
The patent No. is that the Chinese patent of 1429919A " has utilized titanium ore to produce the method for rich titanium material " to disclose the method that improves the titanium slag grade, it is to send in the insulation crystallization oxidized still with titanium slag or without the rich titanium material of the solubility in acid of Raymond mill fine grinding, use electric-arc heating, oxygen blast or oxidized still is heated with oxygen-Fuel lance or oxygen (air) direct current plasma producer, oxygen blast, add silica simultaneously, fluoride additive, titanium slag or the rich titanium material of solubility in acid are carried out the solid phase deep oxidation, form the rich titanium material of rutile, this rich titanium material makes the rutile grain growth in annealer, cooling is after broken, ore grinding and gravity treatment dump mine tailing, obtain TiO
2＞92%～96% low calcium and magnesium artificial rutile.
U.S. mineral office has announced a kind of method that improves the titanium slag grade at " Bureau of Mines Report RI 7985 " in 1970, it is to obtain titanium slag by electric furnace reduction, titanium slag gives oxidation through low temperature, at high temperature add additive through phase oxidative, obtain the rich titanium material of rutile, rich titanium material obtains high-grade artificial rutile through acid dipping separation.
All there is following shortcoming in the above-mentioned method for preparing high-grade artificial rutile:
1. can not effectively utilize high-titanium slag physics heat, energy consumption is big, the production cost height;
2. at solid-state oxidation titanium slag down, the oxidizing roasting time is long, and efficient is low;
3. acidolysis is leached under high temperature, high pressure, and labour intensity is big, and pollution is arranged;
4. oxidation and slow cooling need specific metallurgical furnace, and facility investment is big, complicated operation;
5. technical process is long, and effect is undesirable.
Summary of the invention
The purpose of this invention is to provide a kind of method of utilizing high-titanium slag to produce artificial rutile, this process design is reasonable, equipment is simple, and is easy to operate, makes full use of the energy of raw material self, the thermo-efficiency height, the enrichment that helps titanium component is grown up and alligatoring mutually with rutile, and it is good to separate the rutile phase effect, can significantly improve quality product, and non-environmental-pollution
The object of the present invention is achieved like this: this method adopts following three steps:
One, titanium component selective enrichment:
With the titanium slag heat fused that is contained in the slag ladle, the temperature after the fusing is controlled at 1500-1650 ℃; After homo(io)thermism, in slag ladle, add additive, additive therefor is CaO, MgO, BaO, Na
2O, MnO, Cr
2O
3, Al
2O
3, B
2O
3, SiO
2, P
2O
5, CaF
2,, Na
2B
4O
7Or Na
3PO
4In a kind of or its mixture, the consumption of additive is 3%～9% of a slag total amount, when adding additive or afterwards, jet in the slag gas mixture of air, oxygen, air and oxygen or the gas mixture of air and nitrogen comes dross-oxidised, the weight ratio of oxidization time and titanium slag is subjected to the gas flow effect, be controlled at minute: gram=1: 10～50 scopes, the dividing potential drop of oxygen is controlled at 10 in the gas
-2In-1atm the scope, make titanium component optionally be enriched in rutile mutually in;
Two, the rutile phase selectivity is grown up:
Titanium component optionally be enriched in rutile mutually after, in 1500-1650 ℃ of temperature range, lower the temperature, control rate of temperature fall, make the slag speed of cooling be controlled at 0.5-5 ℃/min scope; Be cooled to room temperature, carry out selectivity and grow up;
Three, the rutile phase selectivity is separated:
Titanium component optionally is enriched in rutile mutually and grow up cooling crust block after the processing of rutile phase selectivity, through broken, levigate, granularity adopts isolating method of hydrometallurgy or the isolating method of ore dressing less than 150 orders, greater than 300 orders, rutile in the crust block is separated out, obtains TiO
2Artificial rutile of high grade.
In the chemical constitution of described slag, the titanyl compound content range is 50-85%.
Add a cover at described slag ladle top, perisporium fill insulant material layer.
During described rutile phase selectivity is separated, adopting the hydrometallurgy separation method is that titanium component optionally is enriched in rutile mutually and grow up cooling crust block after the processing of rutile phase selectivity, after broken, levigate, with mineral acid or regeneration mineral acid extraction separation, leaching condition is: acid concentration is 5～45%, dipping time 10～60 minutes, 30～90 ℃ of dipping temperatures, 4～10 revolutions per seconds of stirring velocitys are separated out with the rutile in the crust block, obtain high-grade artificial rutile.
Described mineral acid or regeneration mineral acid are a kind of or its mixture of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, hydrofluoric acid.
During described rutile phase selectivity is separated, adopting the isolating method of ore dressing is that titanium component optionally is enriched in rutile mutually and grow up cooling crust block after the processing of rutile phase selectivity, after broken, levigate, with gravity treatment, flotation, or gravity treatment is separated out with the rutile in the crust block in conjunction with flotation combined method, obtains high-grade artificial rutile.
Because process design of the present invention is reasonable, make full use of the physics heat of slag self, blow by in slag, spraying into an amount of oxidizing gas, make and go back ortho states material generation exothermic oxidation reaction in the slag, this not only makes the slag temperature raise, promote the carrying out of chemical reaction in the slag, and oxidation can make, and the anosovite phase oxidation is the rutile phase in the slag; Can make the metallic iron droplet congregating carried secretly in the slag, grow up and sedimentation, realize reclaiming.Simultaneously, the adding of additive make be dispersed in the titanium component of different ore deposits in mutually optionally enrichment enter rutile mutually and realize growing up and alligatoring.Therefore, by oxidation with add the measure of additive, control the trend and the pattern that contain titanium component in the slag, thereby create favorable conditions for selective separation.Because rutile is insoluble to mineral acid mutually in the slag, and most of impurity is dissolved in acid in the slag, the titanium slag of oxidation modification goes out to realize rutile and impurity selective separation through acidleach; Also can adopt the isolating method of ore dressing to realize that rutile separates with the gangue phase selectivity.Finally obtain the high-quality product artificial rutile, TiO
2Content reaches more than 85%.
The present invention has following positively effect:
1, the high-titanium slag temperature is more than 1500 ℃, and the physics heat of melting slag is big; Simultaneously, the slag oxidizing reaction discharges a large amount of heat energy, and the slag temperature is raise, and promotes that chemical reaction carries out the utilization efficiency of heat energy height of slag;
2, the oxidizing reaction of slag is carried out in slag ladle, and equipment is simple, easy handling;
3, there is variform (Ti in the valence state of titanium in the titanium slag
2+, Ti
3+And Ti
4+), they be distributed in dispersedly multi mineral mutually in.Wherein, the low price titanium mineral is based on anosovite (about 20～42%).In oxidising process, low price titanium (Ti
2+, Ti
3+) be oxidized to high price titanium (Ti
4+), (Ti in the slag
4+) with rutile phase (TiO
2) the form existence.Therefore, oxidizing reaction help slag at a middle or low price titanium optionally be enriched in rutile mutually in;
4, add the acidic oxide additive in the slag, impel the anosovite phase decomposition, impurity wherein enters the matrix phase; Add the basic oxide additive, can reduce viscosity coefficient of dross, also help rutile and generate mutually;
5, in the slag oxidising process, the slag temperature raises, and viscosity degradation is accelerated oxidation rate, promotes rutile phase evolution reaction (TiO
2)=TiO
2 (S)Carry out to the right, help titanium and optionally be enriched in the rutile phase;
6, in the slag oxidising process, the slag temperature raises, and viscosity reduces, and helps rutile and grows up mutually and alligatoring.In addition, the certain heat-treat condition (soaking time, rate of temperature fall and slag temperature) of control also helps rutile and grows up mutually and alligatoring;
7, rutile is insoluble to mineral acid mutually in the slag, and most of impurity is dissolved in acid in the slag, and the crust block that above-mentioned modification is handled is optionally separated rutile in the slag and impurity after acidleach goes out, and obtains TiO
2The rich titanium material of the artificial rutile of content more than 85%, this is a kind of separation method;
8, in the slag rutile than great, hardness is big, adopts the isolating method of ore dressing, with crust block fragmentation, levigate, use gravity treatment or flotation again, or gravity treatment can be separated out also in conjunction with flotation combined method with the rutile in the crust block
Description of drawings
Below in conjunction with accompanying drawing the present invention is further described.
Fig. 1 is a kind of technical process of the present invention.
Fig. 2 (a) is the back scattering microstructure figure of former slag;
(b) be the back scattering microstructure figure of oxidation sludge.
Fig. 3 (a) is the microscopic appearance figure of oxidization time oxidation sludge when being 1min;
(b) be the microscopic appearance figure of oxidization time oxidation sludge when being 5min.
Embodiment
Describe concrete technical process of the present invention in detail according to Fig. 1-3 and embodiment.This method adopts following three steps:
One, titanium component selective enrichment:
At first take by weighing a certain amount of electrosmelting titanium slag, in the chemical constitution of slag, the titanyl compound content range is 50-85%.The titanium slag that takes by weighing is contained in the slag ladle, and heating makes the slag fusing, and the temperature of slag is controlled at 1500-1650 ℃.After homo(io)thermism, in slag ladle, add additive, additive therefor is CaO, MgO, BaO, Na
2O, MnO, Cr
2O
3, Al
2O
3, B
2O
3, SiO
2, P
2O
5, CaF
2,, Na
2B
4O
7Or Na
3PO
4In a kind of or its mixture, the consumption of additive is 3%～9% of a slag total amount.When adding additive or afterwards, jet in the slag gas mixture of air, oxygen, air and oxygen or the gas mixture of air and nitrogen comes dross-oxidised, the time of oxidation and the weight ratio of slag are subjected to the gas flow effect, be controlled at minute: gram=1: 10～50 scopes, the dividing potential drop of oxygen is controlled at 10 in the gas
-2In-1atm the scope, make titanium component optionally be enriched in rutile mutually in;
Two, the rutile phase selectivity is grown up:
Above-mentioned titanium component optionally be enriched in rutile mutually after, in 1500-1650 ℃ of temperature range, lower the temperature, control rate of temperature fall, make the slag speed of cooling be controlled at 0.5-5 ℃/min scope.When slag was cooled to room temperature with slag ladle, the rutile of selective enrichment titanium component carried out selectivity mutually and grows up.
Three, the rutile phase selectivity is separated:
Above-mentioned titanium component optionally is enriched in rutile mutually and grow up cooling crust block after the processing of rutile phase selectivity, through broken, levigate to granularity be+150 orders～-300 orders, adopt isolating method of hydrometallurgy or the isolating method of ore dressing, the rutile in the crust block is separated out, obtain TiO
2Artificial rutile of high grade.
In the aforesaid operations step,, in slag ladle, carry out oxidising process better, can add a cover perisporium fill insulant material layer at the slag ladle top for making full use of the physics heat of slag.
In the aforesaid operations step, the rutile phase selectivity is separated the hydrometallurgy separation method that adopts: titanium component optionally is enriched in grow up cooling crust block after the processing of rutile phase and rutile phase selectivity, after broken, levigate, with mineral acid or regeneration mineral acid extraction separation, leaching condition is: acid concentration is 5%～45%, dipping time 10～60 minutes, 30～90 ℃ of dipping temperatures, 4～10 revolutions per seconds of stirring velocitys, rutile in the crust block is separated out, obtains high-grade artificial rutile.
In the aforesaid operations step, used mineral acid or regeneration mineral acid are a kind of or its mixture of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, hydrofluoric acid.
In the aforesaid operations step, during separating, the rutile phase selectivity adopt the isolating method of ore dressing to be: titanium component optionally is enriched in rutile mutually and grow up cooling crust block after the processing of rutile phase selectivity, after broken, levigate, with gravity treatment, flotation, or gravity treatment is in conjunction with flotation combined method, rutile in the crust block is separated out, obtains high-grade artificial rutile.
Embodiment 1
Take by weighing the 200g smelting titanium slag with electric stove, its composition is 74.79%TiO
2, 3.14%CaO, 8.89%MgO, 3.86%Al
2O
3, 3.10%FeO.The titanium slag that takes by weighing is contained in the slag ladle, and the heating titanium slag is until fusing, and the slag temperature is controlled at about 1550 ℃; After homo(io)thermism, in the slag of slag ladle, add addition of C aO 6g and P
2O
514g.When adding additive (or afterwards), the oxygen of jetting in slag, oxidization time are 5min, and the dividing potential drop of oxygen is controlled at 10
-2In-1atm the scope, make titanium component optionally be enriched in rutile mutually in.Afterwards, about 40 ℃ because of oxidation raises of the temperature of slag reach 1590 ℃; 1590～1300 ℃ of temperature range inner control speed of cooling is 2 ℃/min, and furnace cooling is to room temperature, and rutile carries out selectivity mutually and grows up.Cooled oxidation crust block, through broken, levigate to granularity be+200 orders～-300 orders.Adopt dilute hydrochloric acid dipping ground-slag, 50 ℃ of dipping temperatures, dipping time 30min, concentration of hydrochloric acid 14%, 4 revolutions per seconds of stir speed (S.S.)s; Ground-slag after the acid dipping is filtered, dries, finally obtain grade 91.26%TiO
2Artificial rutile.
Embodiment 2
Take by weighing the 200g smelting titanium slag with electric stove, its composition is 74.79%TiO
2, 3.14%CaO, 8.89%MgO, 3.86%Al
2O
3, 3.10%FeO.Resistive heating makes the slag fusing, continues to heat up, and when temperature reaches 1550C, steady temperature, aerating oxygen under molten state adds addition of C aO 4g and Na simultaneously
3PO
414g, oxidization time 5min, the dividing potential drop of oxygen is controlled at 10
-2In-1atm the scope, the slag temperature is elevated to 1590 ℃ after the oxidation, lowers the temperature 5 ℃/min of speed of cooling in 1590～1300 ℃ of temperature ranges.Cooled oxidation crust block fragmentation, levigate, granularity+200 orders～-300 orders.Leach 55 ℃ of dipping temperatures, 4 revolutions per seconds of stir speed (S.S.)s, dipping time 40min with 16% hydrochloric acid.After filtration, the oven dry, obtain containing 90.06%TiO at last
2Artificial rutile.
Embodiment 3
Take by weighing the 200g smelting titanium slag with electric stove, its composition is 74.79%TiO
2, 3.14%CaO, 8.89%MgO, 3.86%Al
2O
3, 3.10%FeO.Resistive heating makes the slag fusing, continues to heat up, and when temperature reaches 1530C, steady temperature, aerating oxygen under molten state adds addition of C aF simultaneously
26g and P
2O
512g, oxidization time 5min, the dividing potential drop of oxygen is controlled at 10
-2In-1atm the scope, the slag temperature is elevated to 1570 ℃ after the oxidation.Lower the temperature in 1570～1300 ℃ of temperature ranges, speed of cooling is 1.0 ℃/min.Cooled oxidation crust block fragmentation, levigate, granularity+200 orders～-300 orders.Leach 45 ℃ of dipping temperatures, 4 revolutions per seconds of stir speed (S.S.)s, dipping time 50min with 10% hydrochloric acid.After filtration, the oven dry, obtain containing 89.28%TiO at last
2Artificial rutile.
Embodiment 4
Take by weighing the 200g smelting titanium slag with electric stove, its composition is 74.79%TiO
2, 3.14%CaO, 8.89%MgO, 3.86%Al
2O
3, 3.10%FeO.Resistive heating makes the slag fusing, continues to heat up, and when temperature reaches 1530C, steady temperature, aerating oxygen under molten state adds additive Na simultaneously
2O 4g and P
2O
510g, oxidization time 4min, the dividing potential drop of oxygen is controlled at 10
-2In-1atm the scope, the slag temperature is elevated to 1560 ℃ after the oxidation, lowers the temperature 0.5 ℃/min of speed of cooling in 1560～1300 ℃ of temperature ranges.Cooled oxidation crust block fragmentation, levigate, granularity+150 orders～-200 orders.Adopt reelection and separation method that the rutile in the crust block is separated out, obtain containing 87.3%TiO at last
2Artificial rutile.
Embodiment 5
Take by weighing the 200g smelting titanium slag with electric stove, its composition is 74.79%TiO
2, 3.14%CaO, 8.89%MgO, 3.86%Al
2O
3, 3.10%FeO.Resistive heating makes the slag fusing, continues to heat up, and when temperature reaches 1580C, steady temperature, bubbling air under molten state adds additive B aO 4g and P simultaneously
2O
512g, oxidization time 6min, the dividing potential drop of oxygen is controlled at 10
-2In-1atm the scope, the slag temperature is elevated to 1610 ℃ after the oxidation, lowers the temperature 0.5 ℃/min of speed of cooling in 1610～1300 ℃ of temperature ranges.Cooled oxidation crust block fragmentation, levigate, granularity+150 orders～-200 orders leaches 55 ℃ of dipping temperatures, dipping time 40min, 4 revolutions per seconds of stir speed (S.S.)s with 20% sulfuric acid.After filtration, the oven dry, obtain containing 90.2%TiO at last
2Artificial rutile.
Embodiment 6
Take by weighing the 200g smelting titanium slag with electric stove, its composition is 74.79%TiO
2, 3.14%CaO, 8.89%MgO, 3.86%Al
2O
3, 3.10%FeO.Resistive heating makes the slag fusing, continues to heat up, and when temperature reaches 1560C, steady temperature, aerating oxygen under molten state adds additive Na simultaneously
3PO
412g, oxidization time 4min, the dividing potential drop of oxygen is controlled at 10
-2In-1atm the scope, the slag temperature is elevated to 1590 ℃ after the oxidation, lowers the temperature 0.5 ℃/min of speed of cooling in 1590～1300 ℃ of temperature ranges.Cooled oxidation crust block fragmentation, levigate, granularity+150 orders～-200 orders.Leach 45 ℃ of dipping temperatures, dipping time 30min, 4 revolutions per seconds of stir speed (S.S.)s with 15% sulfuric acid.After filtration, the oven dry, obtain containing 86.4%TiO at last
2Artificial rutile.
Embodiment 7
Take by weighing the 200g smelting titanium slag with electric stove, its composition is 74.79%TiO
2, 3.14%CaO, 8.89%MgO, 3.86%Al
2O
3, 3.10%FeO.Resistive heating makes the slag fusing, continues to heat up, and when temperature reached 1550C, steady temperature fed oxygen-rich air under molten state, add additive Na simultaneously
3PO
418g, oxidization time 5min, the dividing potential drop of oxygen is controlled at 10
-2In-1atm the scope, the slag temperature is elevated to 1570 ℃ after the oxidation, lowers the temperature 5 ℃/min of speed of cooling in 1570～1300 ℃ of temperature ranges.Cooled oxidation crust block fragmentation, levigate, granularity+200 orders～-300 orders.Leach 45 ℃ of dipping temperatures, dipping time 20min, 4 revolutions per seconds of stir speed (S.S.)s with 20% phosphoric acid.After filtration, the oven dry, obtain containing 90.6%TiO at last
2Artificial rutile.
Embodiment 8
Take by weighing the 200g smelting titanium slag with electric stove, its composition is 74.79%TiO
2, 3.14%CaO, 8.89%MgO, 3.86%Al
2O
3, 3.10%FeO.Resistive heating makes the slag fusing, continues to heat up, and when temperature reached 1550C, steady temperature fed oxygen-rich air under molten state, add additive B simultaneously
2O
318g, oxidization time 6min, the dividing potential drop of oxygen is controlled at 10
-2In-1atm the scope, the slag temperature is elevated to 1580 ℃ after the oxidation, lowers the temperature 2 ℃/min of speed of cooling in 1580～1300 ℃ of temperature ranges.Cooled oxidation crust block fragmentation, levigate, granularity+200 orders～-300 orders.Leach 45 ℃ of dipping temperatures, dipping time 30min, 8 revolutions per seconds of stir speed (S.S.)s with 16% phosphoric acid.After filtration, the oven dry, obtain containing 90.2TiO at last
2%.
Embodiment 9
Take by weighing the 200g smelting titanium slag with electric stove, its composition is 74.79%TiO
2, 3.14%CaO, 8.89%MgO, 3.86%Al
2O
3, 3.10%FeO.Resistive heating makes the slag fusing, continues to heat up, and when temperature reaches 1550C, steady temperature, aerating oxygen under molten state adds additive B simultaneously
2O
312g, oxidization time 3min, the dividing potential drop of oxygen is controlled at 10
-2In-1atm the scope, the slag temperature is elevated to 1570 ℃ after the oxidation, lowers the temperature 2 ℃/min of speed of cooling in 1570～1300 ℃ of temperature ranges.Cooled oxidation crust block fragmentation, levigate, granularity+200 orders～-300 orders leaches 45 ℃ of dipping temperatures, dipping time 30min, 8 revolutions per seconds of stir speed (S.S.)s with 20% nitric acid.After filtration, the oven dry, obtain containing 88.15%TiO at last
2Artificial rutile.
Embodiment 10
Take by weighing the 200g smelting titanium slag with electric stove, its composition is 74.79%TiO
2, 3.14%CaO, 8.89%MgO, 3.86%Al
2O
3, 3.10%FeO.Resistive heating makes the slag fusing, continues to heat up, and when temperature reaches 1550C, steady temperature, aerating oxygen under molten state adds additive B aO 16g simultaneously, oxidization time 3min, the dividing potential drop of oxygen is controlled at 10
-2In-1atm the scope, the slag temperature is elevated to 1570 ℃ after the oxidation, lowers the temperature 2 ℃/min of speed of cooling in 1570～1300 ℃ of temperature ranges.Cooled oxidation crust block fragmentation, levigate, granularity+200 orders～-300 orders.Leach with 20% hydrochloric acid, 65 ℃ of dipping temperatures, dipping time 30min, 8 revolutions per seconds of stir speed (S.S.)s after filtration, oven dry, obtain containing 86.9%TiO at last
2Artificial rutile.
Embodiment 11
Take by weighing the 200g smelting titanium slag with electric stove, its composition is 74.79%TiO
2, 3.14%CaO, 8.89%MgO, 3.86%Al
2O
3, 3.10%FeO.Resistive heating makes the slag fusing, continues to heat up, and when temperature reaches 1570C, steady temperature, aerating oxygen under molten state adds addition of C aF simultaneously
212g, oxidization time 5min, the dividing potential drop of oxygen is controlled at 10
-2In-1atm the scope, the slag temperature is elevated to 1610 ℃ after the oxidation, lowers the temperature 0.5 ℃/min of speed of cooling in 1610～1300 ℃ of temperature ranges.Cooled oxidation crust block fragmentation, levigate, granularity+150 orders～-200 orders.Leach 55 ℃ of dipping temperatures, dipping time 40min, 8 revolutions per seconds of stir speed (S.S.)s with 15% hydrochloric acid.After filtration, the oven dry, obtain containing 88.7%TiO at last
2
Embodiment 12
Take by weighing the 200g smelting titanium slag with electric stove, its composition is 74.79%TiO
2, 3.14%CaO, 8.89%MgO, 3.86%Al
2O
3, 3.10%FeO.Resistive heating makes the slag fusing, continues to heat up, and when temperature reached 1560C, steady temperature fed oxygen-rich air under molten state, add additive P simultaneously
2O
512g, oxidization time 6min, the dividing potential drop of oxygen is controlled at 10
-2In-1atm the scope, the slag temperature is elevated to 1590 ℃ after the oxidation, lowers the temperature 3 ℃/min of speed of cooling in 1590～1300 ℃ of temperature ranges.Cooled oxidation crust block fragmentation, levigate, granularity+200 orders～-300 orders leaches with 30% sulfuric acid, 55 ℃ of dipping temperatures, dipping time 30min, 8 revolutions per seconds of stir speed (S.S.)s obtain containing 90.6%TiO at last through filter, oven dry
2Artificial rutile.
Embodiment 13
Take by weighing the 200g smelting titanium slag with electric stove, its composition is 74.79%TiO
2, 3.14%CaO, 8.89%MgO, 3.86%Al
2O
3, 3.10%FeO.Resistive heating makes the slag fusing, continues to heat up, and when temperature reaches 1560C, steady temperature, the gas mixture of bubbling air and nitrogen under molten state adds additive NaF 6g and SiO simultaneously
210g, oxidization time are 12min, and the dividing potential drop of oxygen is controlled at 10
-2In-1atm the scope, the slag temperature is elevated to 1580 ℃ after the oxidation, lowers the temperature 0.5 ℃/min of speed of cooling in 1580～1300 ℃ of temperature ranges.Cooled oxidation crust block is through broken, levigate, granularity+100 orders～-200 orders, and gravity treatment dumps mine tailing, obtains containing 88.3%TiO
2Artificial rutile.
Claims (6)
1. method of utilizing high-titanium slag to produce artificial rutile is characterized in that: adopt following three steps:
One, titanium component selective enrichment:
To be contained in titanium slag in the slag ladle through heat fused, the temperature after the fusing is controlled at 1500-1650 ℃; After homo(io)thermism, in slag ladle, add additive, additive therefor is CaO, MgO, BaO, Na
2O, MnO, Cr
2O
3, Al
2O
3, B
2O
3, SiO
2, P
2O
5, CaF
2, Na
2B
4O
7Or Na
3PO
4In a kind of or its mixture, the consumption of additive is 3%～9% of a slag total amount, when adding additive or afterwards, jet in the slag gas mixture of air, oxygen, air and oxygen or the gas mixture of air and nitrogen comes dross-oxidised, the time of oxidation and the weight ratio of slag are subjected to the gas flow effect, be controlled at minute: gram=1: 10～50 scopes, the dividing potential drop of oxygen is controlled at 10 in the gas
-2In-1atm the scope, make titanium component optionally be enriched in rutile mutually in;
Two, the rutile phase selectivity is grown up:
Titanium component optionally be enriched in rutile mutually after, in 1500-1650 ℃ of temperature range, lower the temperature, control rate of temperature fall, make the slag speed of cooling be controlled at 0.5-5 ℃/min scope; Be cooled to room temperature, carry out selectivity and grow up;
Three, the rutile phase selectivity is separated:
Titanium component optionally is enriched in rutile mutually and grow up cooling crust block after the processing of rutile phase selectivity, through broken, levigate, granularity adopts isolating method of hydrometallurgy or the isolating method of ore dressing less than 150 orders, greater than 300 orders, rutile in the crust block is separated out, obtains TiO
2Artificial rutile of high grade.
2. the method for utilizing high-titanium slag to produce artificial rutile according to claim 1, it is characterized in that: in the chemical constitution of described slag, the titanyl compound content range is 50-85%.
3. the method for utilizing high-titanium slag to produce artificial rutile according to claim 1, it is characterized in that: add a cover at described slag ladle top, perisporium fill insulant material layer.
4. the method for utilizing high-titanium slag to produce artificial rutile according to claim 1, it is characterized in that: adopting the hydrometallurgy separation method during described rutile phase selectivity is separated is that titanium component optionally is enriched in rutile mutually and grow up cooling crust block after the processing of rutile phase selectivity, through fragmentation, after levigate, with mineral acid or regeneration mineral acid extraction separation, leaching condition is: acid concentration is 5%～45%, dipping time 10～60 minutes, 30～90 ℃ of dipping temperatures, 4～10 revolutions per seconds of stirring velocitys, rutile in the crust block is separated out, obtains high-grade artificial rutile.
5. according to claim 1 or the 4 described methods of utilizing high-titanium slag to produce artificial rutile, it is characterized in that: described mineral acid or regeneration mineral acid are a kind of or its mixture of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, hydrofluoric acid.
6. the method for utilizing high-titanium slag to produce artificial rutile according to claim 1, it is characterized in that: adopting the isolating method of ore dressing during described rutile phase selectivity is separated is that titanium component optionally is enriched in rutile mutually and grow up cooling crust block after the processing of rutile phase selectivity, after broken, levigate, with gravity treatment, flotation, or gravity treatment is separated out with the rutile in the crust block in conjunction with flotation combined method, obtains high-grade artificial rutile.
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| CN102154531A (en) * | 2011-03-25 | 2011-08-17 | 喀左县钒钛资源综合开发利用工程技术研究中心 | Method for producing artificial rutile from titanium-containing blast furnace slags |
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| CN102061393B (en) * | 2010-06-18 | 2013-04-10 | 四川龙蟒矿冶有限责任公司 | Titanium slag deep processing method |
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| CN102337413B (en) * | 2011-11-14 | 2013-06-12 | 北京大学 | Method for producing artificial rutile by utilizing titanium-containing blast furnace slag |
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| CN108793238A (en) * | 2017-04-26 | 2018-11-13 | 云南民族大学 | A kind of method that the leaching of microwave calcining phosphoric acid prepares rutile |
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