CN108408767A - A kind of titanium dioxide and the method using titanium-containing blast furnace slag production titanium dioxide - Google Patents
A kind of titanium dioxide and the method using titanium-containing blast furnace slag production titanium dioxide Download PDFInfo
- Publication number
- CN108408767A CN108408767A CN201810361446.5A CN201810361446A CN108408767A CN 108408767 A CN108408767 A CN 108408767A CN 201810361446 A CN201810361446 A CN 201810361446A CN 108408767 A CN108408767 A CN 108408767A
- Authority
- CN
- China
- Prior art keywords
- titanium
- blast furnace
- furnace slag
- calcium
- containing blast
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
- C01G23/0532—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing sulfate-containing salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/02—Particle morphology depicted by an image obtained by optical microscopy
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention relates to metallurgical technology fields, provide a kind of method producing titanium dioxide using titanium-containing blast furnace slag, include the following steps：Molten state titanium-containing blast furnace slag is modified in having oxidizing gas atmosphere with calcium modifying agent, carry out isolated calcium ilmenite concentrate, wherein calcium modifying agent includes calcium oxide and aluminium oxide；Calcium ilmenite concentrate is carried out to acidolysis, the purification of titanium liquid, concentration, hydrolysis, washing, salt treatment and calcining successively and obtains titanium dioxide, acid hemolysis process carries out in the environment of temperature is 95 DEG C~250 DEG C.This method enables to the titanium in titanium-containing blast furnace slag to be recycled utilization to prepare titanium dioxide, and the calcium ilmenite concentrate generated in preparation process is since iron-holder is few or not iron content, iron powder reducing step and iron removal are not required to when for producing titanium dioxide, titanium white production technique, and titanium dioxide composite quality obtained requirement can effectively be simplified.The present invention also provides a kind of titanium dioxides, are made by aforementioned production method.
Description
Technical field
The present invention relates to metallurgical technology fields, and titanium is produced in particular to a kind of titanium dioxide and using titanium-containing blast furnace slag
The method of white powder.
Background technology
Abundant v-ti magnetite ore resources are contained in China's Panxi Diqu and Chengde area, and the reserves of symbiosis account for about the whole nation
The 90.54% of titanium gross reserves.About 53% titanium enters v-ti magnetite concentrate after ore dressing in current production procedure, through blast furnace
After smelting, titanium almost all enters slag phase, forms the blast furnace slag of titaniferous, causes a large amount of titanium-containing blast furnace slag to accumulate, not only wastes
Valuable titanium resource, and pollute environment.
But the recycling of titanium-containing blast furnace slag is can not achieve in existing method substantially, cause a large amount of wasting of resources.
Invention content
The present invention provides a kind of methods producing titanium dioxide using titanium-containing blast furnace slag, it is intended to improve existing titanium-containing blast furnace slag
The problem of the production process complexity of waste and existing titanium dioxide.
The present invention also provides a kind of titanium dioxide, the titanium dioxide quality is more excellent.
The invention is realized in this way：
A method of titanium dioxide being produced using titanium-containing blast furnace slag, is included the following steps：
Molten state titanium-containing blast furnace slag is modified in having oxidizing gas atmosphere with calcium modifying agent, carry out isolated calcium
Ilmenite concentrate, wherein calcium modifying agent includes calcium oxide and aluminium oxide；
Calcium ilmenite concentrate is carried out to acidolysis, the purification of titanium liquid, concentration, hydrolysis, washing, salt treatment and calcining successively and obtains titanium white
Powder, acid hemolysis process carry out in the environment of temperature is 95 DEG C~250 DEG C.
Further, in preferred embodiments of the present invention, acid hemolysis process use mass concentration for 89~94% sulfuric acid.
Further, in preferred embodiments of the present invention, the mass ratio of calcium ilmenite concentrate and sulfuric acid is 1:1.18~1.24.
Further, in preferred embodiments of the present invention, the dosage of calcium oxide is titanium-containing blast furnace slag in calcium modifying agent
The 3~4% of quality.
Further, in preferred embodiments of the present invention, the dosage of aluminium oxide is the 1~3% of titanium-containing blast furnace slag quality.
Further, in preferred embodiments of the present invention, molten state titanium-containing blast furnace slag modification postcooling is taken on furnace body
Portion's substance is 70~80 μm by being ground to grain diameter, calcium ilmenite concentrate is obtained through gravity treatment.
Further, in preferred embodiments of the present invention, molten state titanium-containing blast furnace slag temperature is 1300 DEG C~1400 DEG C.
Further, in preferred embodiments of the present invention, oxidizing gas is oxygen-containing gas, and in oxidizing gas
Oxygen content is 30~50%, and it is 1.5-2.5L/min that gas, which is passed through rate,.
Further, in preferred embodiments of the present invention, acid hemolysis process is not use iron powder after dissolving calcium ilmenite concentrate
Ferric iron in reduction of dissolved liquid is up to titanium liquid.
A kind of titanium dioxide is made using the above-mentioned method for producing titanium dioxide using titanium-containing blast furnace slag.
The beneficial effects of the invention are as follows：The present invention produces titanium dioxide by what above-mentioned design obtained using titanium-containing blast furnace slag
Method, due to its by blast furnace slag by calcium modifier modification after, the few calcium ilmenite concentrate of isolated iron content so that in titanium
It need not remember that titanium liquid, titanium liquid obtained exist in white powder production process after acidolysis with the ferric ion in iron powder reducing lysate
Also it is not required to freezing and crystallizing in purification process and removes iron therein, not only so that titanium-containing blast furnace slag is fully used, is produced from centre
Object calcium ilmenite concentrate is for manufacturing titanium dioxide, moreover it is possible to so that production process of titanium pigment is more simple and convenient, and by made from this method
Titanium dioxide quality meets titanium dioxide quality requirement with titanium dioxide quality made from existing method.
Description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is shape appearance figure of the blast furnace slag before modified under 100 power microscopes；
Fig. 2 is shape appearance figure of the corresponding modified blast furnace slag of embodiment 6 under 100 power microscopes；
Fig. 3 is shape appearance figure of the corresponding modified blast furnace slag of embodiment 7 under 100 power microscopes；
Fig. 4 is shape appearance figure of the corresponding modified blast furnace slag of embodiment 8 under 100 power microscopes；
Fig. 5 is shape appearance figure of the corresponding modified blast furnace slag of embodiment 9 under 100 power microscopes；
Fig. 6 is shape appearance figure of the corresponding modified blast furnace slag of embodiment 10 under 100 power microscopes；
Fig. 7 is shape appearance figure of the corresponding modified blast furnace slag of embodiment 11 under 100 power microscopes.
Specific implementation mode
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, builds according to normal condition or manufacturer
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Below to the embodiment of the present invention provide it is a kind of using titanium-containing blast furnace slag produce titanium dioxide method illustrate.
A method of titanium dioxide being produced using titanium-containing blast furnace slag, is included the following steps：
It is S1, molten state titanium-containing blast furnace slag is modified in having oxidizing gas atmosphere with calcium modifying agent, detach
To calcium ilmenite concentrate, wherein calcium modifying agent includes calcium oxide and aluminium oxide.
Temperature is at 1300 DEG C or more after titanium-containing blast furnace slag is generally come out of the stove, content of titanium dioxide about 20% or so, but in stove
The distribution of titanium more disperses in slag, is unfavorable for carrying out later use.
Calcium modifying agent is added in the molten state titanium-containing blast furnace slag for being 1300 DEG C~1400 DEG C to stove body temperature, to titaniferous height
Clinker is modified, and oxidizing gas is passed through in modifying process.The modifying agent of calcic and high temperature furnace slag exist under the high temperature conditions
Calcium titanium alloy is formed under molten condition, this part calcium titanium alloy is largely focused on the top of furnace body, main in the lower part of furnace body
Iron-containing mineral are formed, centre is waste minerals, and the modification blast furnace slag of upper of furnace body is filtered out by longitudinal ore dressing.Then will divide
First cool down from obtained modification blast furnace slag, perovskite crystal grain made to grow up, then by be ground to grain diameter be 70~80 μm, through weight
Choosing throws tail and selects calcium ilmenite concentrate.
It is more than 70 μm since modified slag perovskite average grain diameter is increased to modified major part by 20 μm before modified, modified slag
Perovskite average grain diameter is up to 70~80 μm.The perovskite of modified slag is set all to reach 80% or so monomer, their ore grinding grain
The degree upper limit should reach 60 μm or so.When blast furnace (modification) slag grinding particle size upper limit is 40 μm, perovskite monomer that slag dissociates
96.89% can be reached.In contrast, under the conditions of identical perovskite liberation degree of minerals, unmodified blast furnace slag, thin mud inventory
High, expendable grade inventory increases considerably.By modification, titanium component can be enriched in titanium-containing blast furnace slag
To Perovskite Phase, titanium degree of enrichment reaches 80%, and 35 μm of perovskite minimum grain size, most of to be more than 70 μm, maximum is up to 700 μm.
Further, control stove body temperature is about 1300 degree, modification time about 0.5h.The temperature of titanium-containing blast furnace slag is
The temperature of 1200-1500 DEG C, preferably 1300-1400 DEG C, titanium-containing blast furnace slag should control in a certain range, to promote returning for titanium
Rate is received, the enrichment of titanium is accelerated.
Specifically, calcium modifying agent includes calcium oxide and aluminium oxide, and inventor has found that calcium oxide and aluminium oxide is used for calcium to change
Titanium can be enriched with out by property agent to a greater extent to be recycled, and the rate of recovery of titanium is very high.Wherein, the addition of aluminium oxide can drop
The viscosity of low melt improves processing condition, and Perovskite Phase is promoted to grow up.
Further, the dosage of calcium oxide is the 3~4% of titanium-containing blast furnace slag quality in calcium modifying agent, oxygen in modifying agent
The dosage for changing aluminium is the 1~3% of titanium-containing blast furnace slag quality.Inventor has found substantially to control in the quality of calcium oxide and aluminium oxide
Impurity content is minimum in above range, in obtained calcium ilmenite concentrate and the utilization rate highest of titanium.
Preferably, for other oxygen contents of the oxidisability 30~50%, it is 1.5-2.5L/min timeliness that gas, which is passed through rate,
Fruit is best.Oxygen-containing gas can be air, but control oxygen content therein, unsuitable too low or excessively high, the content of content
The too low oxidation effectiveness that will appear titanium is undesirable, not fully oxidized, and then influences the quality of calcium ilmenite concentrate；The excessively high meeting of oxygen content
The oxidation rate for appearing in titanium in modifying process is too fast, and increase cost while be easy to cause the waste of gas.
Preferably, during with calcium modifier modification, it is passed through oxidizing gas oxidation 5-8min.Lead in modifying process
Entering oxidizing gas can make Low-valent Titanium be oxidized to titanic, improve the purity of the rate of recovery and calcium ilmenite concentrate of titanium.Oxidization time
Need control in a certain range, fully oxidized, the another aspect oxidization time that on the one hand to ensure that the titanium component in titanium slag obtains
The long adherency that can lead to slag becomes larger, and is unfavorable for growing up for perovskite crystal grain.
S2, calcium ilmenite concentrate is carried out successively acidolysis, titanium liquid purification, concentration, hydrolysis, washing, salt treatment and calcining obtain
Titanium dioxide, acid hemolysis process carry out in the environment of temperature is 95 DEG C~250 DEG C.
Specifically, calcium ilmenite concentrate made from S1 steps is subjected to acidolysis first and obtains titanium liquid, acidolysis use mass concentration for
89~94% sulfuric acid, the sulfuric acid of the concentration can make in calcium ilmenite concentrate can vitriolization substance obtain it is molten to the greatest extent
Solution.Further, the mass ratio of calcium ilmenite concentrate and sulfuric acid is 1:1.18~1.24, under the conditions of the ratio, calcium ilmenite concentrate can fill
Divide the waste that is dissolved in sulfuric acid and can utmostly avoid sulfuric acid.
The reaction equation of acid hemolysis process is as follows：
CaTiO3(s)+2H2SO4(l)=CaSO4↓(s)+TiOSO4(s)+2H2O(g)
CaTiO3(s)+3H2SO4(l)=CaSO4↓(s)+Ti(SO4)2(s)+3H2O(l)(H2SO4It is excessive)
CaO(s)+H2SO4(l)=CaSO4↓(s)+H2O(g)
MgO(s)+H2SO4(l)=MgSO4(s)+H2O(g)
Al2O3(s)+3H2SO4(l)=Al2(SO4)3(s)+3H2O(g)
FeO(s)+H2SO4(l)=FeSO4(s)+H2O(g)
It is obtained since calcium ilmenite concentrate is that titanium-containing blast furnace slag is modified, wherein iron content and its small, due to iron and sulfuric acid reaction
Heat release, since ilmenite concentrate iron content is higher in traditional ilmenite concentrate titanium dioxide technique, acid hemolysis process heat release makes it no longer need to
External complement heat, and the calcium ilmenite concentrate that iron content that the present invention uses is few, the heat that iron contained therein is released with sulfuric acid reaction
Amount is not enough to provide main reaction institute calorific requirement, therefore needs additional additional heat in this programme to ensure that reaction is smoothed out.
Therefore acid hemolysis process needs to heat, and ensures that acid hemolysis process carries out in the environment of temperature is 95 DEG C~250 DEG C, to lure acidolysis reaction
It carries out.
Further, due in S1 calcium ilmenite concentrate iron-holder seldom be directly used in fire titanium dioxide after wherein iron content also exist
In acceptability limit, relative to the existing technique for producing titanium dioxide using ilmenite concentrate, production method provided by the invention does not need
Iron powder is added into titanium liquid makes ferric ion therein restore, therefore the titanium liquid obtained after acidolysis directly carries out next step titanium liquid
Purification.
The purification of titanium liquid includes the processes such as sedimentation, separation, filtering.Sedimentation agent is added into titanium liquid, which is mainly
Flocculant makes titanium liquid preliminary purification to remove insoluble impurities in titanium liquid and colloidal solid.
In conventional processes, since it uses the higher raw material of iron-holder, therefore it uses iron powder mentioned above by trivalent
Iron is reduced to ferrous iron, and the precipitation step through step same as described above after reduction is needed by freezing and crystallizing to remove wherein later
Iron.And since iron content is few in this programme, therefore be not required to crystallize after settling, directly carry out separating step.
Separation, filtering are detached by centrifuge, filter and three processes of plate compression are constituted.Titanium liquid through centrifuge detach and
It filters pond to filter, obtains the diluted Ti solution of preliminary purification, finally by diluted Ti solution by plate compression, obtain meeting the clear of production needs
Titanium liquid.
Clear titanium liquid is concentrated, using continous way thin film evaporator, is evaporated under conditions of reduced vacuum in titanium liquid
Moisture content, to meet the needs of hydrolyzing process.
Titanium liquid after concentration includes water, titanium dioxide and sulfuric acid, it is allowed to carry out in a heated condition
It is general using introducing in order to promote the progress of hydrolysis, and the hydrated titanium dioxide made to meet the requirements to metatitanic acid
Crystal seed or automatic growing crystal species.
The task of washing is to detach metatitanic acid with mother liquor, be washed with water wash it is miscellaneous to eliminate contained solubility in metatitanic acid
Matter.
Salt treatment is carried out after cleaning, is carried out in salt treatment pot.In the case where being sufficiently stirred, add into metatitanic acid slurries
Enter the salt treatment agents such as potassium carbonate and phosphoric acid, calcining materials can be prevented to be sintered, the colour developing of hidden impurity element makes calcination product particle
It is soft, color and luster is pure white etc..
Metatitanic acid is placed in rotary kiln after salt treatment and is calcined, through processes such as high temperature dehydration, desulfurization and transformation of crystal,
Obtain the titanium dioxide with pigment performance.
A kind of titanium dioxide is made using the method provided by the invention for producing titanium dioxide using titanium-containing blast furnace slag.
Below in conjunction with specific embodiment titanium dioxide is produced to a kind of titanium dioxide provided by the invention and using titanium-containing blast furnace slag
Method be specifically described.
Embodiment 1
An embodiment of the present invention provides a kind of method producing titanium dioxide using titanium-containing blast furnace slag, operating procedure is as follows：
The molten state titanium-containing blast furnace slag that temperature is 1300 DEG C~1400 DEG C is modified with calcium modifying agent in furnace body, is changed
Property the time be 0.5h, the gas that oxygen quality percentage composition is 30% is passed through into furnace body while modified, gas is passed through speed
Rate is 1.5L/min, is passed through oxidization time as 5min, calcium oxide content is the 3% of blast furnace slag quality in calcium modifying agent, modifying agent
The dosage of middle aluminium oxide is the 1% of titanium-containing blast furnace slag quality.The modification blast furnace slag of upper of furnace body is screened after the completion of modifying process, so
After allow modified blast furnace slag to cool down, so that calcium mine crystal grain is grown up, then be ground to grain diameter in 70~80 μ ms, tail thrown through gravity treatment
Select calcium ilmenite concentrate.
Then by calcium ilmenite concentrate through carrying out acidolysis, the purification of titanium liquid, concentration, hydrolysis, washing, salt treatment successively and calcining
To titanium dioxide, acid hemolysis process carries out in the environment of temperature is 95 DEG C.Above-mentioned acidolysis, the purification of titanium liquid, concentration, hydrolysis, washing,
Salt treatment and the concrete operations mode of calcining step are joined particular content in above-mentioned S2, wherein sulfuric acid used by acid hemolysis process
Mass concentration is 89%, and the mass ratio of calcium ilmenite concentrate and sulfuric acid is 1:1.18.
Embodiment 2
An embodiment of the present invention provides a kind of method producing titanium dioxide using titanium-containing blast furnace slag, operating procedure is as follows：
The molten state titanium-containing blast furnace slag that temperature is 1300 DEG C~1400 DEG C is modified with calcium modifying agent in furnace body, is changed
Property the time be 0.5h, the gas that oxygen quality percentage composition is 40% is passed through into furnace body while modified, gas is passed through speed
Rate is 2.5L/min, is passed through oxidization time as 8min, calcium oxide content is the 4% of blast furnace slag quality in calcium modifying agent, modifying agent
The dosage of middle aluminium oxide is the 3% of titanium-containing blast furnace slag quality.The modification blast furnace slag of upper of furnace body is screened after the completion of modifying process, so
After allow modified blast furnace slag to cool down, so that calcium mine crystal grain is grown up, then be ground to grain diameter in 70~80 μ ms, tail thrown through gravity treatment
Select calcium ilmenite concentrate.
Then by calcium ilmenite concentrate through carrying out acidolysis, the purification of titanium liquid, concentration, hydrolysis, washing, salt treatment successively and calcining
To titanium dioxide, acid hemolysis process carries out in the environment of temperature is 250 DEG C.Above-mentioned acidolysis, the purification of titanium liquid, concentration, hydrolysis, water
It washes, the concrete operations mode of salt treatment and calcining step is joined by particular content in above-mentioned S2, wherein used by acid hemolysis process
H 2 so 4 concentration is 94%, and the mass ratio of calcium ilmenite concentrate and sulfuric acid is 1:1.24.
Embodiment 3
An embodiment of the present invention provides a kind of method producing titanium dioxide using titanium-containing blast furnace slag, operating procedure is as follows：
The molten state titanium-containing blast furnace slag that temperature is 1300 DEG C~1400 DEG C is modified with calcium modifying agent in furnace body, is changed
Property the time be 0.5h, the gas that oxygen quality percentage composition is 32% is passed through into furnace body while modified, gas is passed through speed
Rate is 2L/min, is passed through oxidization time as 6min, calcium oxide content is the 3.2% of blast furnace slag quality in calcium modifying agent, modifying agent
The dosage of middle aluminium oxide is the 2.7% of titanium-containing blast furnace slag quality.The modification blast furnace slag of upper of furnace body is screened after the completion of modifying process,
Then it allows modified blast furnace slag to cool down, so that calcium mine crystal grain is grown up, then be ground to grain diameter in 70~80 μ ms, thrown through gravity treatment
Tail selects calcium ilmenite concentrate.
Then by calcium ilmenite concentrate through carrying out acidolysis, the purification of titanium liquid, concentration, hydrolysis, washing, salt treatment successively and calcining
To titanium dioxide, acid hemolysis process carries out in the environment of temperature is 100 DEG C.Above-mentioned acidolysis, the purification of titanium liquid, concentration, hydrolysis, water
It washes, the concrete operations mode of salt treatment and calcining step is joined by particular content in above-mentioned S2, wherein used by acid hemolysis process
H 2 so 4 concentration is 90%, and the mass ratio of calcium ilmenite concentrate and sulfuric acid is 1:1.2.
Embodiment 4
An embodiment of the present invention provides a kind of method producing titanium dioxide using titanium-containing blast furnace slag, operating procedure is as follows：
The molten state titanium-containing blast furnace slag that temperature is 1300 DEG C~1400 DEG C is modified with calcium modifying agent in furnace body, is changed
Property the time be 0.5h, the gas that oxygen quality percentage composition is 35% is passed through into furnace body while modified, gas is passed through speed
Rate is 1.8L/min, is passed through oxidization time as 7min, calcium oxide content is the 3.5% of blast furnace slag quality in calcium modifying agent, modified
The dosage of aluminium oxide is the 1.5% of titanium-containing blast furnace slag quality in agent.The modification blast furnace of upper of furnace body is screened after the completion of modifying process
Then slag allows modified blast furnace slag to cool down, so that calcium mine crystal grain is grown up, then be ground to grain diameter in 70~80 μ ms, through weight
Choosing throws tail and selects calcium ilmenite concentrate.
Then by calcium ilmenite concentrate through carrying out acidolysis, the purification of titanium liquid, concentration, hydrolysis, washing, salt treatment successively and calcining
To titanium dioxide, acid hemolysis process carries out in the environment of temperature is 150 DEG C.Above-mentioned acidolysis, the purification of titanium liquid, concentration, hydrolysis, water
It washes, the concrete operations mode of salt treatment and calcining step is joined by particular content in above-mentioned S2, wherein used by acid hemolysis process
H 2 so 4 concentration is 91%, and the mass ratio of calcium ilmenite concentrate and sulfuric acid is 1:1.19.
Embodiment 5
An embodiment of the present invention provides a kind of method producing titanium dioxide using titanium-containing blast furnace slag, operating procedure is as follows：
The molten state titanium-containing blast furnace slag that temperature is 1300 DEG C~1400 DEG C is modified with calcium modifying agent in furnace body, is changed
Property the time be 0.5h, the gas that oxygen quality percentage composition is 37% is passed through into furnace body while modified, gas is passed through speed
Rate is 2.3L/min, is passed through oxidization time as 6.5min, calcium oxide content is the 3.8% of blast furnace slag quality in calcium modifying agent, is changed
Property agent in aluminium oxide dosage be titanium-containing blast furnace slag quality 2.5%.The modified high of upper of furnace body is screened after the completion of modifying process
Then clinker allows modified blast furnace slag to cool down, so that calcium mine crystal grain is grown up, then be ground to grain diameter in 70~80 μ ms, pass through
Gravity treatment throws tail and selects calcium ilmenite concentrate.
Then by calcium ilmenite concentrate through carrying out acidolysis, the purification of titanium liquid, concentration, hydrolysis, washing, salt treatment successively and calcining
To titanium dioxide, acid hemolysis process carries out in the environment of temperature is 220 DEG C.Above-mentioned acidolysis, the purification of titanium liquid, concentration, hydrolysis, water
It washes, the concrete operations mode of salt treatment and calcining step is joined by particular content in above-mentioned S2, wherein used by acid hemolysis process
H 2 so 4 concentration is 93%, and the mass ratio of calcium ilmenite concentrate and sulfuric acid is 1:1.23.
Embodiment 6
An embodiment of the present invention provides a kind of method producing titanium dioxide using titanium-containing blast furnace slag, operating procedure is as follows：
The molten state titanium-containing blast furnace slag that temperature is 1300 DEG C~1400 DEG C is modified with calcium modifying agent in furnace body, is changed
Property the time be 0.5h, the gas that oxygen quality percentage composition is 40% is passed through into furnace body while modified, gas is passed through speed
Rate is 2.4L/min, is passed through oxidization time as 6min, calcium oxide content is the 4% of blast furnace slag quality in calcium modifying agent, modifying agent
The dosage of middle aluminium oxide is the 2% of titanium-containing blast furnace slag quality.The modification blast furnace slag of upper of furnace body is screened after the completion of modifying process, so
After allow modified blast furnace slag to cool down, so that calcium mine crystal grain is grown up, then be ground to grain diameter in 70~80 μ ms, tail thrown through gravity treatment
Select calcium ilmenite concentrate.
Then by calcium ilmenite concentrate through carrying out acidolysis, the purification of titanium liquid, concentration, hydrolysis, washing, salt treatment successively and calcining
To titanium dioxide, acid hemolysis process carries out in the environment of temperature is 180 DEG C.Above-mentioned acidolysis, the purification of titanium liquid, concentration, hydrolysis, water
It washes, the concrete operations mode of salt treatment and calcining step is joined by particular content in above-mentioned S2, wherein used by acid hemolysis process
H 2 so 4 concentration is 90%, and the mass ratio of calcium ilmenite concentrate and sulfuric acid is 1:1.2.
Embodiment 7
The present embodiment is roughly the same with embodiment 6, the difference is that calcium modifier component proportioning is different, wherein oxidation
The dosage of calcium is the 1% of titanium-containing blast furnace slag, and the dosage of aluminium oxide is the 1% of titanium-containing blast furnace slag.
Embodiment 8
The present embodiment is roughly the same with embodiment 6, the difference is that calcium modifier component proportioning is different, wherein oxidation
The dosage of calcium is the 2% of titanium-containing blast furnace slag, and the dosage of aluminium oxide is the 1% of titanium-containing blast furnace slag.
Embodiment 9
The present embodiment is roughly the same with embodiment 6, the difference is that calcium modifier component proportioning is different, wherein oxidation
The dosage of calcium is the 3% of titanium-containing blast furnace slag, and the dosage of aluminium oxide is the 1% of titanium-containing blast furnace slag.
Embodiment 10
The present embodiment is roughly the same with embodiment 6, the difference is that calcium modifier component proportioning is different, wherein oxidation
The dosage of calcium is the 4% of titanium-containing blast furnace slag, and the dosage of aluminium oxide is the 1% of titanium-containing blast furnace slag.
Embodiment 11
The present embodiment is roughly the same with embodiment 6, the difference is that calcium modifier component proportioning is different, wherein oxidation
The dosage of calcium is the 3% of titanium-containing blast furnace slag, and the dosage of aluminium oxide is the 2% of titanium-containing blast furnace slag.
Experimental example 1
Blast furnace slag before modified 100 times of microstructures as shown in Figure 1, different calcium amount of modifier pair in testing example 6-11
As a result the influence of Perovskite Phase grain size and degree of enrichment is shown in that Fig. 2-Fig. 7, Fig. 2-Fig. 7 are respectively embodiment 6-11 right respectively respectively
The modified shape appearance figure positioned at the modification blast furnace slag of upper of furnace body under 100 power microscopes answered, white portion is calcium titanium in figure
Mine phase.
By Fig. 2-7 it is found that working as modifying agent CaO 4%, Al2O3When 2%, perovskite grain size is high with degree of enrichment, and calcium
Titanium ore crystal grain is uniform.With this condition, Spinel disappears substantially.
Test example 2
The element composition of titanium-containing blast furnace slag and modified modification blast furnace slag in testing example 5 before modified is ground
Study carefully, sees Tables 1 and 2.
The element composition (wt%) of different phase regions in the former slag of table 1 EDX analyses
Table 2：EDX analyzes modified blast furnace slag not element composition (mass fraction) in jljl alpha region
By Tables 1 and 2 it is found that the main preservation of titanium there are no titanium in Perovskite Phase in magnesium aluminate spinel phase in slag；Matrix
The mass fraction average out to 8.157% or so of phase region titanium component, the numerical value are higher than the titanium component quality that titandiopside is climbed in former slag
Score average 3.26%, less than the titanium component mass fraction average value of rich titandiopside in former slag, in general, modified height
Ti content of the Ti content of clinker matrix phase significantly lower than former slag matrix phase before modified.It is, the modified big portion for making matrix phase
Titanium is divided to shift and be enriched in Perovskite Phase.Degree of enrichment result of calculation shows that 80% or more titanium component is enriched to Perovskite Phase,
Moreover, mine phase composition becomes simpler, only perovskite, magnesium aluminate spinel and phase containing titanaugite.Calcium ilmenite concentrate is to pass through modification
The ground gravity treatment of blast furnace slag is made, by not iron content in calcium titanium phase known to upper table, therefore calcium ilmenite concentrate made from final grinding gravity treatment
In not iron content or iron content it is extremely low, almost can be ignored.
In conclusion a kind of production method of titanium dioxide based on blast furnace slag provided by the invention, since it is by blast furnace slag
After calcium modifier modification, the few calcium ilmenite concentrate of isolated iron content so that in the acidolysis in production process of titanium pigment
It need not remember that titanium liquid, titanium liquid obtained are also not required to cold in purification process with the ferric ion in iron powder reducing lysate afterwards
Freeze brilliant removal iron therein, not only so that titanium-containing blast furnace slag is fully used, by intermediate product calcium ilmenite concentrate for manufacturing
Titanium dioxide, moreover it is possible to so that production process of titanium pigment is more simple and convenient, and pass through titanium dioxide quality made from this method and existing side
Titanium dioxide quality made from method meets titanium dioxide quality requirement.
The foregoing is merely the preferred embodiment of the present invention, are not intended to restrict the invention, for this field
For technical staff, the invention may be variously modified and varied.All within the spirits and principles of the present invention, any made by
Modification, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of method producing titanium dioxide using titanium-containing blast furnace slag, which is characterized in that include the following steps：
Molten state titanium-containing blast furnace slag is modified in having oxidizing gas atmosphere with calcium modifying agent, carry out isolated calcium titanium essence
Mine, wherein the calcium modifying agent includes calcium oxide and aluminium oxide；
The calcium ilmenite concentrate is subjected to acidolysis, the purification of titanium liquid, concentration, hydrolysis, washing, salt treatment and calcining successively and obtains titanium white
Powder, the acid hemolysis process carry out in the environment of temperature is 95 DEG C~250 DEG C.
2. the method according to claim 1 for producing titanium dioxide using titanium-containing blast furnace slag, which is characterized in that the acidolysis
The sulfuric acid that Cheng Caiyong mass concentrations are 89~94%.
3. the method according to claim 2 for producing titanium dioxide using titanium-containing blast furnace slag, which is characterized in that the calcium titanium essence
The mass ratio of mine and the sulfuric acid is 1:1.18~1.24.
4. the method according to claim 1 for producing titanium dioxide using titanium-containing blast furnace slag, which is characterized in that change in the calcium
Property agent described in calcium oxide dosage be the titanium-containing blast furnace slag quality 3~4%.
5. the method according to claim 4 for producing titanium dioxide using titanium-containing blast furnace slag, which is characterized in that the aluminium oxide
Dosage be the titanium-containing blast furnace slag quality 1~3%.
6. the method according to claim 1 for producing titanium dioxide using titanium-containing blast furnace slag, which is characterized in that by the melting
State titanium-containing blast furnace slag is modified postcooling and takes upper of furnace body substance, is 70~80 μm by being ground to grain diameter, is obtained through gravity treatment
The calcium ilmenite concentrate.
7. the method according to claim 1 for producing titanium dioxide using titanium-containing blast furnace slag, which is characterized in that the molten state
Titanium-containing blast furnace slag temperature is 1300 DEG C~1400 DEG C.
8. the method according to claim 1 for producing titanium dioxide using titanium-containing blast furnace slag, which is characterized in that the oxidisability
Gas is oxygen-containing gas, and the oxygen content in the oxidizing gas is 30~50%, and it is 1.5-2.5L/ that gas, which is passed through rate,
min。
9. the method according to claim 1 for producing titanium dioxide using titanium-containing blast furnace slag, which is characterized in that the acidolysis
Journey is not use the ferric iron in iron powder reducing lysate up to titanium liquid after dissolving the calcium ilmenite concentrate.
10. a kind of titanium dioxide, which is characterized in that utilize titanium-containing blast furnace slag production using such as claim 1-9 any one of them
The method of titanium dioxide is made.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810361446.5A CN108408767A (en) | 2018-04-20 | 2018-04-20 | A kind of titanium dioxide and the method using titanium-containing blast furnace slag production titanium dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810361446.5A CN108408767A (en) | 2018-04-20 | 2018-04-20 | A kind of titanium dioxide and the method using titanium-containing blast furnace slag production titanium dioxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108408767A true CN108408767A (en) | 2018-08-17 |
Family
ID=63136225
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810361446.5A Pending CN108408767A (en) | 2018-04-20 | 2018-04-20 | A kind of titanium dioxide and the method using titanium-containing blast furnace slag production titanium dioxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108408767A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20220127159A1 (en) * | 2018-12-14 | 2022-04-28 | Avertana Limited | Methods of extraction of products from titanium-bearing materials |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86108511A (en) * | 1986-12-10 | 1988-06-22 | 中南工业大学 | Produce the method for titanium dioxide with the titaniferous iron-smelting blast-furnace slag |
| CN1743386A (en) * | 2005-09-27 | 2006-03-08 | 四川大学 | Method for preparing pigment-level titanium powder and coarse titanium white from blast slag containing titanium |
| CN102050487A (en) * | 2010-12-31 | 2011-05-11 | 攀钢集团重庆钛业有限公司 | Acidolysis method in titanium dioxide production technology adopting sulfuric acid process |
-
2018
- 2018-04-20 CN CN201810361446.5A patent/CN108408767A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86108511A (en) * | 1986-12-10 | 1988-06-22 | 中南工业大学 | Produce the method for titanium dioxide with the titaniferous iron-smelting blast-furnace slag |
| CN1743386A (en) * | 2005-09-27 | 2006-03-08 | 四川大学 | Method for preparing pigment-level titanium powder and coarse titanium white from blast slag containing titanium |
| CN102050487A (en) * | 2010-12-31 | 2011-05-11 | 攀钢集团重庆钛业有限公司 | Acidolysis method in titanium dioxide production technology adopting sulfuric acid process |
Non-Patent Citations (1)
| Title |
|---|
| 马腾: ""低钛型高炉渣中含钛组分的析出与长大"", 《中国优秀硕士学位论文全文数据库》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20220127159A1 (en) * | 2018-12-14 | 2022-04-28 | Avertana Limited | Methods of extraction of products from titanium-bearing materials |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2743355C1 (en) | Method of extracting vanadium from vanadium slag with high content of calcium and phosphorus | |
| CN104313361B (en) | A kind of Leaching of Vanadium from Vanadium slag containing chromium and the process of coproduction chromium-base alloy | |
| JP5792727B2 (en) | Concentrated titanium hydrochloric acid extraction residue, its use and method for preparing titanium pigment | |
| CN102154531B (en) | Method for producing artificial rutile from titanium-containing blast furnace slags | |
| CN109355515B (en) | Method for extracting vanadium by calcified vanadium extraction tailings | |
| RU2365649C1 (en) | Method of recovery of vanadium from titanium-vanadium slag | |
| CN107032400B (en) | TiCl4The method that purification tailings alkali is soaked standby high-purity vanadium oxide | |
| CN111534706A (en) | Method for preparing titanium-rich material from Panxi titanium concentrate | |
| CN104310467B (en) | Comprehensive utilization method of high titanium slag | |
| CN103194603A (en) | Preparation method of high-purity vanadium pentoxide | |
| CN101812595A (en) | Method for producing artificial rutile from titanium slag | |
| CN103922423B (en) | A kind of method utilizing titanium white waste acid to improve v slag grade | |
| CN107267766B (en) | A method of Selective Separation vanadium, titanium, iron from modified vanadium slag | |
| CN110016548A (en) | The method of vanadium titano-magnetite concentrate roasting extraction vanadium extraction | |
| CN108408767A (en) | A kind of titanium dioxide and the method using titanium-containing blast furnace slag production titanium dioxide | |
| US2417101A (en) | Titaniferous magnetite treatment | |
| CN108358237A (en) | A kind of titanium dioxide and the titanium white production method based on titanium-containing blast furnace slag | |
| AU759721B2 (en) | Method of smelting copper sulfide concentrate | |
| FR2604428A1 (en) | PROCESS FOR PREPARING VANADIUM PENTOXIDE | |
| CN110423893A (en) | The method that titanium tetrachloride purification tailings prepares vanadic sulfate | |
| CN109680158A (en) | A method of Titanium or titanium white are prepared using titanium-contained slag | |
| NO333502B1 (en) | Process for treating titanium slag prepared from ilmenite in beach sand | |
| JP3682166B2 (en) | Method for smelting copper sulfide concentrate | |
| CN107653380A (en) | It is a kind of to regulate and control to melt the method for dividing titanium slag crystallization phase | |
| CN112391537A (en) | Method for extracting vanadium by using hydrochloric acid, sulfuric acid and vanadium-containing high-calcium high-phosphorus slag |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180817 |
|
| RJ01 | Rejection of invention patent application after publication |