CN101597082A - From titaniferous materials, extract the method for titanium dioxide - Google Patents
From titaniferous materials, extract the method for titanium dioxide Download PDFInfo
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Abstract
A kind of method of extracting titanium dioxide from titaniferous materials such as blast furnace slag, ilmenite or titanium slag comprises hydrogen bromide solution dissolving blast furnace slag, alkaline purification filtrate and separates TiO
2With SiO
2Deng three steps, wherein, hydrogen bromide can recycle, and starts reaction and gets final product so only need to add enough hydrogen bromides and raw material in the initial stage.The present invention is the method for a kind of economy, efficient and environment amenable extraction titanium dioxide.
Description
Technical field
The present invention relates to a kind of method of from titaniferous materials, extracting titanium dioxide, particularly from blast furnace slag, ilmenite and titanium slag, extract the method for titanium dioxide.
Background technology
Titanium dioxide is commonly called as titanium white or titanium dioxide.Have good physics and chemical property (molten boiling point is high, stability is strong, adhesive power is strong, color is extremely white, nontoxic etc.), titanium dioxide is a kind of important chemical material and daily or industrial coating, often is used to make refractory glass, glaze, enamel, potter's clay, resistant to elevated temperatures experimental ware etc.Global titanium dioxide output was 5,000,000 tons in 2006, and was increasing with annual 3～5% speed.China is titanium white production and consumption big country, and titanium dioxide output reached about 700,000 tons in 2005, estimated will reach more than 1,200,000 tons in 2008, will become the second-biggest-in-the-world titanium white production state that is only second to the U.S..Titanium dioxide mainly contains two kinds of chemical structures: Detitanium-ore-type and rutile-type, at present, main commercial titanium dioxide is a rutile-type.
Except traditional titaniferous materials, at present there are some large-scale iron and steel enterprises all producing a large amount of blast furnace slags every day in the world, iron-smelting raw material will become the blast furnace slag that is rich in titanium dioxide (typical content is 15%～35%) comparatively speaking after having experienced special refining program.In these iron and steel enterprises, the foremost Panzhihua Iron (hereinafter to be referred as climbing steel) that is China.Since 1970 firstly appear, climb steel and produced 5,000 ten thousand tons of blast furnace slags altogether, at present still with every year nearly 3,000,000 tons speed increasing.Climb in the blast furnace slag of steel and contain 21%～23% titanium dioxide, also contain silicon-dioxide, calcium oxide, aluminum oxide, magnesium oxide and some other a small amount of compound.If the titanium dioxide in these blast furnace slags can be extracted, its economic worth will be huge.But, because it is quite complicated, with high costs to extract the process of titanium dioxide from blast furnace slag, so, up to now, still do not have cost-effective method and from blast furnace slag, extract titanium dioxide.Blast furnace slag is not fully utilized, and can only be used for material of construction at present.And how storing these blast furnace slags all is a difficult problem for iron and steel enterprise, and a large amount of blast furnace slags is piled up and also environment also caused influence.
At occurring in nature, titaniferous ore has several different natural existence forms: natural rutile, ilmenite.90%～95% titanium dioxide is contained in the natural rutile ore deposit, but this ore is worldwide more and more rare; Ilmenite contains 35%～65% titanium dioxide, and common working method is that ilmenite is processed into the titanium slag that is rich in titanium dioxide.It is SORELSLAG that one of titanium slag supplier's advanced in the world QIT-Fer et Titane (QIT) makes the trade mark, contain the titanium dioxide amount is about 80% titanium slag product.This titanium slag is used for Production By Sulfuric Acid Process titanium dioxide.In sulfuric acid process, ilmenite after careful pulverizing and sorting or titanium slag and strong sulfuric acid response obtain titanous sulfate and ferric sulfate, with titanous sulfate separation, calcining, drying, finally obtain titanium dioxide.In addition, QIT has also developed a kind of UGS by name
TMNovel titanium slag product, its titanium dioxide amount is about 94.5%, this titanium slag is mainly used in chlorination process and produces in the titanium dioxide.In chlorination process, titanium slag obtains titanium tetrachloride with chlorine reaction, and titanium tetrachloride obtains titanium dioxide with oxygen reaction.In part country (such as China), directly be raw material often with the ilmenite, adopt Production By Sulfuric Acid Process titanium dioxide, the titanium dioxide quality that this method is not only produced is low, and, can produce the sewage that contains sulfate radical and other by products in a large number in process of production, cause serious environmental to pollute, sulfuric acid also can't recycle, has further aggravated pollution level.
Table 1 is that present industrial use is contained the ore of titanium dioxide and the brief summary that slag extracts the method for titanium dioxide.Sulfuric acid process and chlorination process are industrial two kinds of methods commonly used, and sulfuric acid process power consumption is big and have greater environmental impacts, and be particularly all the more so when it is used to contain the lower raw material of titanium dioxide amount; Chlorination process also has its restriction, and it is only comparatively effective to rich titanium ore slag or natural rutile ore deposit, and when raw material used poor titanium slag or ilmenite, chlorination process needed a large amount of chlorine and is attended by a large amount of metal chloride byproducts.
Table 1
| Sulfuric acid process | Chlorination process | |
| Raw material | Titanium slag (～80% titanium dioxide) ilmenite (35～65% titanium dioxide) | Titanium slag (～95% titanium dioxide) |
| Use chemical feedstocks | Sulfuric acid (dense) | Chlorine |
| Shortcoming | The water consumption is many, and refuse and by product are many, contaminate environment. | Should not adopt ilmenite as raw material |
Summary of the invention
The purpose of this invention is to provide a kind of efficient, free of contamination method of from titaniferous materials, extracting titanium dioxide.
A kind of method of from titaniferous materials, extracting titanium dioxide, it may further comprise the steps:
A) raw material is mixed with aqueous solution of hydrogen bromide, obtain containing liquid and solid mixture;
B) product of filtration step a, separate solid and liquid;
C), obtain containing liquid and solid mixture with gained solid and alkali reaction among the step b;
D) product of filtration step c obtains titanium dioxide.
In the above-mentioned steps, described raw material comprises at least a in blast furnace slag, ilmenite or the titanium slag.
In the above-mentioned steps, the content of titanium dioxide is greater than 10% in the described raw material, and generally speaking, blast furnace slag contains 15～35% titanium dioxide; Ilmenite contains 35～65% titanium dioxide; Titanium slag contains 65～95% titanium dioxide.
In the above-mentioned steps, the temperature range when described raw material mixes with aqueous solution of hydrogen bromide is 100～300 ℃, is preferably 150～250 ℃.
In the above-mentioned steps, the reaction times of described raw material and aqueous solution of hydrogen bromide is 1～15h, is preferably 2～8h.
In the above-mentioned steps, described alkali is preferably sodium hydroxide.
Described method is summarised as, when the raw material that contains titanium dioxide and hydrogen bromide after reaction under the specified temp, can produce titanium dioxide and silicon-dioxide, remaining metal oxide all changes metal bromide into and is dissolved in water with the form of salt; Can obtain titanium dioxide and silicon-dioxide after the filtration, add sodium hydroxide solution again and remove silicon-dioxide, silicon-dioxide and sodium hydroxide solution reaction generate sodium silicate solution, the promptly separable titanium dioxide that obtains.
In the above-mentioned steps, make following two kinds of operating method specifically to be arranged the recycled step of hydrogen bromide thereby can also include treatment step b gained liquid:
First kind of method that reclaims hydrogen bromide:
E), hydrogen bromide is separated with metal bromide with water with liquid evaporation;
F) with among the step e to hydrogen bromide and water be returned among the step a;
G) with the metal bromide and the water vapour reaction that obtain among the step e, obtain metal oxide and hydrogen bromide;
H) hydrogen bromide that obtains in the step g is returned among the step a.
Second kind of method that reclaims hydrogen bromide:
I) in liquid, add enough alkali, the hydrogen bromide in the neutralising fluid, and with the metal bromide reaction, generate precipitate metal hydroxides and metal bromide solution;
J) precipitation that step I is obtained and metal bromide solution separating;
K) with the throw out evaporate to dryness that obtains among the step j;
L) the metal bromide solution that obtains among the electrolysis step j obtain bromine gas and hydrogen, and solution becomes alkaline solution, and this alkaline solution is returned among the rapid i;
M) hydrogen and the bromine solid/liquid/gas reactions that obtains in the step 1 obtained hydrogen bromide, and hydrogen bromide is returned to step a.
In the above-mentioned steps, described alkali is preferably sodium hydroxide.
With respect to prior art, the present invention has series of advantages.
The present invention all is suitable for for the different raw material of content of titanium dioxide.
The present invention adopts hydrogen bromide solution to dissolve to contain the raw material of titanium dioxide, and in this process, hydrogen bromide can recycle, and therefore, only needs to add enough hydrogen bromides and raw material in the initial stage and starts reaction and get final product.
Generally speaking, the present invention is the method for a kind of economy, efficient and environment amenable extraction titanium dioxide.
Description of drawings
Accompanying drawing 1 is a kind of schematic flow sheet of the present invention;
Accompanying drawing 2 is the selectable schematic flow sheet of another kind of the present invention;
Accompanying drawing 3 is the XRD figure spectrum of resulting titanium dioxide among the present invention after calcining under 800 ℃.
Accompanying drawing 4 is the XRD figure spectrum of resulting titanium dioxide among the present invention after calcining under 600 ℃.
Accompanying drawing 5 is an XRD figure spectrum of handling the titanium dioxide of gained under the different condition.
Embodiment
The present invention relates to a kind of novel method of utilizing hydrogen bromide to extract titanium dioxide from titaniferous materials, distinguishingly, these titaniferous materials can be blast furnace slag, ilmenite and titanium slag.In the method, hydrogen bromide recycles, and comprises the step of several recovery hydrogen bromides in this method.
Accompanying drawing 1 has provided a kind of schema of the present invention, and accompanying drawing 2 is another kind of flow processs of the present invention, and the difference of accompanying drawing 2 and accompanying drawing 1 only is to reclaim the step of hydrogen bromide.
In the flow process of accompanying drawing 1, the blast furnace slag, ilmenite or the titanium slag that contain titanium dioxide are at first ground to having the particulate of appropriate particle size.
Raw material is ground to form the particulate with appropriate particle size, it is mixed with aqueous solution of hydrogen bromide and inserts in the closed reactor, carry out smoothly, need to add enough hydrogen bromide solutions for making reaction,
Following reaction takes place in hydrogen bromide and raw material under suitable temperature:
CaO+2HBr＝CaBr
2+H
2O
Al
2O
3+6HBr＝2AlBr
3+3H
2O
MgO+2HBr＝MgBr
2+H
2O
FeO+2HBr＝FeBr
2+H
2O
Fe
2O
3+6HBr＝2FeBr
3+3H
2O
After above-mentioned reaction finished, solid residue was mainly titanium dioxide and silicon-dioxide, all metal bromide (CaBr
2, AlBr
3, MgBr
2, and FeBr
2/ FeBr
3) all water-soluble.
After reaction finishes, filter the gained reaction product, obtain solid residue and the metal bromination salts solution formed by titania/silica.With sending in another reactor that sodium hydroxide is housed after the solid residue cleaning, in this reactor, silicon-dioxide and sodium hydroxide reaction obtain sodium silicate aqueous solution, and after reaction was finished, the filtering reaction product obtained solid titanium dioxide and sodium silicate aqueous solution.Use some ordinary methods from sodium silicate aqueous solution, to obtain silicon-dioxide, for example: obtain yellow soda ash and silica gel in the sodium silicate solution thereby carbonic acid gas can be fed.
Introduce the hydrogen bromide recovery process in accompanying drawing 1 flow process below in detail.
With metal bromination salts solution evaporate to dryness, obtain metal bromide, with metal bromide and steam reaction, obtain metal oxide and hydrogen bromide, above-mentioned reaction can obtain most bromide anions from metal bromide, still, still have a spot of bromide anion to remain in the metal oxide.In order to make full use of the bromine in the metal bromide, thus can be in reactor aerating oxygen or air and bromide anion reaction generate bromine gas, bromine gas and hydrogen reaction generation hydrogen bromide.All HBr/H that generate in the said process
2Thereby O is all returned and finish the hydrogen bromide circulation of system with raw material reaction.
The reaction process of above-mentioned metal bromide and water vapor is:
CaBr
2+H
2O↑/(g)＝CaO+2HBr
2AlBr
3+3H
2O↑/(g)＝Al
2O
3+6HBr
MgBr
2+H
2O↑/(g)＝MgO+2HBr
2FeBr
2+3H
2O↑/(g)＝Fe
2O
3+4HBr+H
2
2Fe
2Br
3+3H
2O↑/(g)＝Fe
2O
3+6HBr
The oxidizing reaction of bromide anion is in the above-mentioned metal oxide:
2CaBr
2+O
2＝2CaO+2Br
2
4AlBr
3+3O
2＝2Al2O
3+6Br
2
2MgBr
2+O
2＝2MgO+2Br
2
4FeBr
2+3O
2＝2Fe2O
3+4Br
2
2Fe
2Br
3+O
2＝2Fe2O
3+3Br
2
Following mask body is set forth the hydrogen bromide working cycle in accompanying drawing 2 flow processs.
Add enough sodium hydroxide in metal bromination salts solution, sodium hydroxide is with remaining hydrogen bromide (NaOH+HBr=NaBr+H
2O) and metal bromide reaction.Generate ironic hydroxide, calcium hydroxide, magnesium hydroxide, aluminium hydroxide and some other a spot of precipitate metal hydroxides.Reaction equation is as follows:
CaBr
2+2NaOH＝Ca(OH)
2↓(s)+2NaBr
AlBr
3+3NaOH＝Al(OH)
3↓(s)+3NaBr
MgBr
2+2NaOH＝Mg(OH)
2↓(s)+2NaBr
FeBr
2+2NaOH＝Fe(OH)
2↓(s)+2NaBr
Fe2Br
3+3NaOH＝Fe(OH)
3↓(s)+3NaBr
After above-mentioned gained precipitation drying, product serves many purposes.For example, when using blast furnace slag, can generate a large amount of Ca (OH) as raw material
2, Al (OH)
3, Mg (OH)
2, and a spot of Fe (OH)
2/ Fe (OH)
3Precipitation, these products can be as the material of making cement.And when using ilmenite or titanium slag, can generate a large amount of Fe (OH) as raw material
2/ Fe (OH)
3And a spot of Ca (OH)
2, Al (OH)
3, Mg (OH)
2Precipitation, these products can be used for smelting iron.
The sodium bromide solution that electrolysis generates, react as follows:
Anode: 2Br
-→ Br
2+ 2e
Negative electrode: 2H
2O+2e → 2OH
-+ H
2
Total reaction: 2NaBr (aq.)+2H
2O → 2Na
+(aq.)+2OH
-(aq.)+Br
2(g)+H
2(g)
The sodium hydroxide solution that generates can be back to the utilization of upper level reaction cycle, and the bromine gas and the hydrogen reaction of generation obtain hydrogen bromide, and hydrogen bromide is back in the reactor that raw material is housed, and realizes recycle.
Following example will further specify the present invention.
Embodiment 1
In the present embodiment, as the chemical ingredients such as table 2 signal of the blast furnace slag of raw material.
Table 2
| Component | Content (mass percent) |
| TiO 2 | ～22％ |
| SiO 2 | ～24％ |
| CaO | ～28％ |
| MgO | ～8％ |
| Al 2O 3 | ～13％ |
| FeO/Fe 2O 3 | ～2.5％ |
| V 2O 5 | ～0.5％ |
| Other | ～2％ |
Before reaction, blast furnace slag is screened with 40 mesh sieves.
Be reflected in the hydrothermal reaction kettle that can tolerate 4MPa and 200 ℃ and carry out, because hydrogen bromide is a kind of corrosive acid that has, so, on the inwall of hydrothermal reaction kettle, need to be provided with the PTFE liner.The reactor capacity is 300mL, at room temperature adds 149.9g concentration and be 40% hydrogen bromide solution, 6.0254g blast furnace slag in reactor, and sealed reactor is warming up to 180 ℃, keeps 4h, is cooled to room temperature then.The filtering reaction product obtains the main solid residue of being made up of titanium dioxide and silicon-dioxide, and above-mentioned solid residue is cleaned and sends in the baking oven dry, the heavy 2.6151g of final product, titanium dioxide and silica recovery are 43.4%.
The above-mentioned final product of 2.5748g is inserted in the hydrothermal reaction kettle of a 100mL, add 5.9201g sodium hydroxide and 80mL water simultaneously.Sealed reactor, reacting by heating still to 180 ℃ is kept 4h, and reactor is cooled to room temperature, and the filtering reaction products therefrom obtains throw out and sodium silicate solution, and above-mentioned sedimentary main component is titanium dioxide.The gained sediment undergoes washing is calcined 2h down at 800 ℃ then, can obtain the titanium dioxide of 1.1202g.This means that the content of titanium dioxide that obtains accounts for 18.6% of blast furnace slag, consider to contain 22% the titanium dioxide of having an appointment in the blast furnace slag raw material that so, the rate of recovery of titanium dioxide is about 85% in the present embodiment.Accompanying drawing 3 is the XRD figure (adopting Bruker, the D8-Advance test) of the titanium dioxide that obtains in the present embodiment, and the result shows that resulting titanium dioxide almost all is rutile crystal type and does not have other dephasigns.
Insert above-mentioned blast furnace slag and reaction of hydrogen bromide after-filtration gained filtrate in the furnace pot and evaporate to dryness to remove moisture and unnecessary hydrogen bromide, obtain metal bromide, metal bromide is inserted fixed-bed reactor and be heated to 600 ℃, in the said fixing bed bioreactor, feed water vapor, continue 4h to obtain HBr; Then fixed-bed reactor are heated to 700 ℃ and aerating oxygen and remain Br with oxidation
-, obtain Br
2And metal oxide.Collect reaction gained Br
2And make it pass through cooling room and and H
2Reaction is to obtain hydrogen bromide.Resulting all hydrogen bromides all are collected and can be used for reacting next time in the said process, and the hydrogen bromide cyclic utilization rate of whole process is 97.31%.
Embodiment 2
The blast furnace slag raw material is at first ground and is screened by 325 mesh sieves.
At room temperature add 35.2g concentration in the reactor and be 40% hydrogen bromide solution, 8.001g blast furnace slag, sealed reactor is heated to 200 ℃ and continue 4h with reactor, is cooled to room temperature then.The filtering reaction product obtains solid precipitation and filtrate.The main component of described solid precipitation is titanium dioxide and silicon-dioxide, above-mentioned solid residue cleaned and sends in the baking oven dry, and the heavy 3.581g of final product, titanium dioxide and silica recovery are 44.76%.
The above-mentioned final product of 3.570g is inserted in the hydrothermal reaction kettle of a 100mL, add 2.695g sodium hydroxide and 20mL water simultaneously.Sealed reactor, reacting by heating still to 180 ℃ is kept 4h, and reactor is cooled to room temperature, and the filtering reaction products therefrom obtains throw out and sodium silicate solution, and above-mentioned sedimentary main component is titanium dioxide.The gained sediment undergoes washing is calcined 2h down at 600 ℃ then, can obtain the titanium dioxide of 1.600g.The rate of recovery of titanium dioxide is about 95% in the present embodiment.Because the reactant in whole process is well controlled, the loss of solids in twice filtration can be ignored, so the rate of recovery is higher.Accompanying drawing 4 is the XRD figure (adopting Bruker, the D8-Advance test) of the titanium dioxide that obtains in the present embodiment, and the result shows that resulting titanium dioxide is rutile-type, Detitanium-ore-type and unformed mixture.
Embodiment 3
The blast furnace slag raw material is at first ground and is screened by 325 mesh sieves.
At room temperature add 35.2g concentration in the hydrothermal reaction kettle of 300ml and be 40% hydrogen bromide solution, 8.000g blast furnace slag, sealed reactor is heated to 200 ℃ and continue 2h with reactor, is cooled to room temperature then.The filtering reaction product obtains solid precipitation and filtrate.The main component of described solid precipitation is titanium dioxide and silicon-dioxide, above-mentioned solid residue cleaned and sends in the baking oven dry, and the heavy 3.643g of final product, titanium dioxide and silica recovery are 45.54%.
Embodiment 4
The blast furnace slag raw material is at first ground and is screened by 325 mesh sieves.
Use five withstand voltage as 4MPa, heat-resisting be 200 ℃ hydrothermal reaction kettle, the capacity of each reactor is 300mL, adds 35.00g concentration under the room temperature and be 40% hydrogen bromide solution, 8.000g blast furnace slag in each reactor.Sealed reactor is heated to 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃ and lasting 4h respectively with five reactors, is cooled to room temperature then.The filtering reaction product obtains solid precipitation and filtrate.The main component of described solid precipitation is titanium dioxide and silicon-dioxide, above-mentioned solid residue is cleaned and sends in the baking oven dry, thereby products therefrom is weighed and is calculated unreacted solid residue, result's meaning as shown in table 3:
Table 3
| Experiment | Blast furnace slag quality (g) | Temperature of reaction (℃) | Solid residue quality (g) | Unreacted solid residue (%) |
| 1 | 8.000 | 120 | 3.938 | 49.22 |
| 2 | 8.000 | 140 | 3.726 | 46.58 |
| 3 | 8.000 | 160 | 3.752 | 46.90 |
| 4 | 8.000 | 180 | 3.802 | 47.53 |
| 5 | 8.000 | 200 | 3.618 | 45.22 |
Embodiment 5
In order to verify the efficient of from metal bromide, extracting bromine, adopt the metal bromide of buying to carry out oxidation test.Select the main component after Calcium Bromide, aluminum bromide, magnesium bromide come the analog blast furnace slag by the hydrogen bromide dissolving for use.Weigh by the composition in the table 4, the metal bromide mixture is placed fixed-bed reactor, feed the pressurized air of capacity, slowly be warming up to 700 ℃ and keep 2h, collect the bromine gas that produces and carry out the water-bath cooling, after reaction finished, the resulting bromine gas of weighing was to calculate reaction yield.Carry out revision test four times, the result shows: at 700 ℃, metal bromide changes the transformation efficiency of metal oxide into more than 97%.
Table 4
| Experiment | AlBr 3· 6H 2O(g) | CaBr 2· 2H 2O(g) | MgBr 2· 6H 2O(g) | Oxidizing temperature (℃) | Transformation efficiency (%) |
| 1 | 0.8433 | 0.7819 | 0.3180 | 700 | 97.52 |
| 2 | 0.8397 | 0.7829 | 0.3175 | 700 | 97.44 |
| 3 | 0.8454 | 0.7824 | 0.3236 | 700 | 97.42 |
| 4 | 0.8455 | 0.7803 | 0.3278 | 700 | 97.60 |
Embodiment 6:
The ilmenite that uses has chemical ingredients as shown in table 5
Table 5
| Component | Content (mass percent) |
| TiO 2 | 47.0％ |
| SiO 2 | 4.3％ |
| CaO | 1.2％ |
| MgO | 4.5％ |
| Al 2O 3 | 1.2％ |
| FeO/Fe 2O 3 | 40.8％ |
| V 2O 5 | 0.7％ |
| Other | 0.3％ |
Grind ilmenite and pass through the screening of 200 mesh sieves.
Use capacity to be 300mL and can anti-4MPa and 200 ℃ hydrothermal reaction kettle, the hydrogen bromide solution and the 8.000g ilmenite that add 43.73g 40%, sealed reactor, be heated to 200 ℃ and lasting 10h, then reactor is cooled to room temperature and opens, the filtering reaction product is isolated solid sediment.The main component of above-mentioned solid sediment is titanium dioxide and silicon-dioxide, cleans solid sediment and insert in the stove to dry, and final weight is 4.023g, TiO
2/ SiO
2The rate of recovery is 50.29%.
It is the hydrothermal reaction kettle of 100mL that the above-mentioned titania/silica throw out of getting 2.000g places a capacity, 1.270g sodium hydroxide and 20mL water are inserted hydrothermal reaction kettle, sealed reactor, be heated to 180 ℃ and lasting 4h, be cooled to room temperature then, the filtering reaction product, obtain solid sediment and sodium silicate solution, the main component of this solid sediment is a titanium dioxide, solid sediment is cleaned and dry down at 120 ℃, finally obtain 1.809g titanium dioxide, this shows has 45% titanium dioxide to obtain recovery in the ilmenite.Because contain 47% titanium dioxide in the ilmenite of raw material, the rate of recovery of titanium dioxide has reached 96%.Adopt xrd method (Bruker, D8-Advance) the resulting titanium dioxide of analytical reaction (selecting the samples of not calcining and under 800 ℃, calcine 2h respectively for use), the result anticipates as shown in Figure 5, as can be seen, resulting product mainly is a rutile titanium dioxide, the anatase titanium dioxide that has trace, and 800 ℃ calcining obviously helps titanium dioxide to form rutile crystal type.
Embodiment 7
Grind ilmenite and pass through the screening of 200 mesh sieves.
Use three capacity to be 300mL and can anti-4MPa and 200 ℃ hydrothermal reaction kettle, add 35.00g, concentration respectively and be 40% hydrogen bromide and 8.000g ilmenite, seal three reactors, be heated to 200 ℃ and continue 4,6 respectively, 8h, then reactor is cooled to room temperature and opens, the filtering reaction product is isolated solid sediment.The main component of above-mentioned solid sediment is titanium dioxide and silicon-dioxide, cleans solid sediment and insert in the stove to dry resulting final product meaning as shown in table 6:
Table 6
| Experiment | Ilmenite quality (g) | Reaction times (h) | Solid residue quality (g) | Unreacted solid residue (%) |
| 1 | 8.000 | 4 | 4.256 | 53.19 |
| 2 | 8.000 | 6 | 4.211 | 52.76 |
| 3 | 8.000 | 8 | 4.111 | 51.83 |
Claims (10)
1. extract the method for titanium dioxide from titaniferous materials, it may further comprise the steps:
A) titaniferous materials is mixed with aqueous solution of hydrogen bromide, obtain containing liquid and solid product;
B) product of filtration step a, thereby separate solid and liquid;
C), obtain containing liquid and solid product with gained solid and alkali reaction among the step b;
D) product of filtration step c obtains titanium dioxide.
2. according to claim 1, described titaniferous materials comprises at least a in blast furnace slag, ilmenite or the titanium slag.
3. according to claim 1, the temperature range when described titaniferous materials mixes with aqueous solution of hydrogen bromide is 100～300 ℃.
4. according to claim 3, the temperature range when described titaniferous materials mixes with aqueous solution of hydrogen bromide is 150～250 ℃.
5. according to claim 1, the reaction times of described titaniferous materials and aqueous solution of hydrogen bromide is 1～15h.
6. according to claim 5, the reaction times of described titaniferous materials and aqueous solution of hydrogen bromide is 2～8h.
7. according to claim 1, make the recycled step of hydrogen bromide thereby also include treatment step b gained liquid.
8. according to claim 7, the step of described treatment liq is:
E), thereby hydrogen bromide is separated with metal bromide with water with liquid evaporation;
F) with among the step e to hydrogen bromide and water be returned among the step a;
G) with the metal bromide and the water vapour reaction that obtain among the step e, obtain metal oxide and hydrogen bromide;
H) hydrogen bromide that obtains in the step g is returned among the step a.
9. according to claim 7, the step of described treatment liq is:
I) in liquid, add alkali, generate precipitate metal hydroxides and metal bromide solution;
J) precipitation that step I is obtained and metal bromide solution separating;
K) the metal bromide solution that obtains among the electrolysis step j obtains bromine gas and hydrogen;
L) hydrogen and the bromine solid/liquid/gas reactions that obtains among the step k obtained hydrogen bromide, and hydrogen bromide is returned to step a.
10. according to claim 1 or 9, described alkali is sodium hydroxide.
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| CN103347646B (en) * | 2011-02-08 | 2015-12-02 | 株式会社神户制钢所 | Welding material raw titanium oxide material |
| CN108220518A (en) * | 2018-02-05 | 2018-06-29 | 高师敏 | A kind of high-chromic vanadium-titanium ferroferrite smelting process and device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012001700A1 (en) * | 2010-06-30 | 2012-01-05 | Keki Hormusji Gharda | Process for extracting metals from aluminoferrous titanoferrous ores and residues |
| US8540951B2 (en) | 2010-06-30 | 2013-09-24 | Keki Hormusji Gharda | Process for extracting metals from aluminoferrous titanoferrous ores and residues |
| CN103347646B (en) * | 2011-02-08 | 2015-12-02 | 株式会社神户制钢所 | Welding material raw titanium oxide material |
| US9527168B2 (en) | 2011-02-08 | 2016-12-27 | Kobe Steel, Ltd. | Titanium oxide raw material for welding material |
| CN108220518A (en) * | 2018-02-05 | 2018-06-29 | 高师敏 | A kind of high-chromic vanadium-titanium ferroferrite smelting process and device |
| CN108220518B (en) * | 2018-02-05 | 2019-12-24 | 高师敏 | Smelting method and device for high-chromium vanadium titano-magnetite |
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