CN108483488A - It is a kind of to produce the crystal seed of rutile, the enrichment method of modifying agent and synthetic rutile using titanium slag - Google Patents
It is a kind of to produce the crystal seed of rutile, the enrichment method of modifying agent and synthetic rutile using titanium slag Download PDFInfo
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Abstract
The crystal seed of rutile, the enrichment method of modifying agent and synthetic rutile being produced using titanium slag the invention discloses a kind of, is related to metallurgical technology field.The enrichment method of the synthetic rutile, includes the following steps：It is heated after titanium slag is mixed with titanium dioxide, oxygen-containing gas is passed through under 1,500 1700 DEG C of temperature condition and carries out 6 12min of oxidation processes；Modifying agent is added after the oxidising treat-ment, then starts to cool down；Wherein, modifying agent includes silica, and 8% 15% that the dosage of silica is titanium slag dosage, and preferably 10% 12%.The titanium in titanium slag can be fully recycled, does not generate the high impurity of environmental pollution degree, obtains the rutile product of high degree of enrichment, there is good market application prospect.
Description
Technical field
The present invention relates to metallurgical technology fields, and more particularly to a kind of crystal seed, modifying agent producing rutile using titanium slag
And the enrichment method of synthetic rutile.
Background technology
The primary chemical group of natural rutile becomes TiO2, general TiO2Content is between 93.5% -98.5%, the main place of production
Concentrate on the states such as Australia, South Africa.Rutile is good Ti industry raw material, but with the rapid development of Ti industry, golden red
Stone resource have the tendency that it is increasingly exhausted, then people just utilize ilmenite concentrate or titanium slag obtained after artificially handling titaniferous grade compared with
High material, i.e. " synthetic rutile ", it is a kind of artificial rich-titanium material, titaniferous amount (TiO2Meter) it is generally higher than 85%.It is artificial
Rutile is used for chloridising production titanium dioxide and Titanium, can also be used as manufacture welding rod and metallurgical raw material etc., is high-quality
Ti industry raw material.
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.The raw material for producing synthetic rutile is largely using ilmenite concentrate as raw material, and small part is titanium slag.With
When ilmenite concentrate is raw material, most of is all the activation process such as to be aoxidized, restored to concentrate, is then cleaned again by acidleach, most
After filter, dry, calcine.And using titanium slag as raw material come when producing synthetic rutile, be mostly be heat-treated, chemistry leach
TiO after the processes such as calcium and magnesium impurity2Grade can be increased to 95% by 80%.Synthetic rutile is produced using ilmenite as raw material to exist
Acid consumption is big, and environmental protection pressure is big, and waste acid treatment is difficult and investment is big, and equipment anticorrosion is difficult, and product has no production cost advantage.And
Synthetic rutile is produced by raw material of titanium slag, due to that two kinds of elements of Fe, Ti in ilmenite are successful during producing titanium slag
Separation, content of titanium dioxide is high in titanium slag, acid consumption is few, and environmentally friendly bring also is greatly reduced while reducing production cost
Adverse effect.
Invention content
The first object of the present invention is to provide a kind of crystal seed being produced rutile using titanium slag, can be given birth to as titanium slag
The crystal seed for producing rutile, obtains the rutile of high degree of enrichment.
The second object of the present invention is to provide a kind of modifying agent being produced rutile using titanium slag, can made in titanium slag
Titanium component be enriched in Rutile Type, obtain the Rutile Type of high degree of enrichment.
The third object of the present invention is to provide a kind of enrichment method of synthetic rutile, can fully recycle titanium
Titanium in slag prepares the rutile of high degree of enrichment.
The present invention solves its technical problem using following technical scheme to realize.
A kind of crystal seed producing rutile using titanium slag, including crystal seed that titanium dioxide is enriched with as rutile, it is preferable that titanium
White powder is rutile type titanium white, and titanium dioxide dosage is the 0.1%-2.0%, preferably 0.5%-1.0% of titanium slag.
The present invention proposes a kind of modifying agent silica producing rutile using titanium slag, and the dosage of silica is
The 8%-15% of titanium slag dosage, preferably 10%-12%.
The present invention also proposes a kind of enrichment method of synthetic rutile, includes the following steps：
After titanium slag is mixed with titanium dioxide crystal seed, it is passed through oxygen-containing gas under 1500-1700 DEG C of temperature condition and carries out oxygen
Change processing 6-12min；Modifying agent is added after the oxidising treat-ment, then starts to cool down.Wherein, crystal seed is titanium dioxide, preferably golden red
Stone-type titanium dioxide, and the 0.1%-2.0%, preferably 0.5%-1.0% that titanium dioxide dosage is titanium slag；Modifying agent includes titanium dioxide
Silicon, and the 8%-15%, preferably 10%-12% that the dosage of silica is titanium slag dosage；
Preferably, titanium dioxide is rutile type titanium white, and titanium dioxide dosage is the 0.1%-2.0% of titanium slag, preferably
0.5%-1.0%.
The present invention also provides a kind of advantageous effects of the enrichment method of synthetic rutile to be：It is using titanium slag as raw material, first
Titanium slag is mixed with titanium dioxide, titanium dioxide plays guiding role, is then passed through under 1500-1700 DEG C of temperature condition oxygenous
Body is aoxidized, and converts lower valency titanium to titanic, and then decrease temperature crystalline is precipitated under the action of silica modified dose, obtains
To the Rutile Type of high degree of enrichment.Therefore, the enrichment method of synthetic rutile provided by the invention can fully recycle titanium
Titanium in slag, recovery method energy conservation and environmental protection do not generate the high impurity of environmental pollution degree, and the purity of product is high, has fine
Market application prospect.
In titanium slag titanium component removal process, extraneous crystal seed plays the role of rutile template direction, makes the titanium group in titanium slag
Divide and rutile is produced into titanium dioxide template；Silica modified dose can make the titanium component in titanium slag be enriched to Rutile Type
In, impurity element releases to form magma cell from anosovite；When the dosage of silica is controlled 10% or so
When be modified in slag and only contain Rutile Type and glass phase, the degree of enrichment of Rutile Type reaches 86%.
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 the X-ray diffracting spectrum of unoxidized titanium slag raw material and 1530 DEG C of high-temperature oxydation product；
Fig. 2 is the degree of enrichment result figure of the Rutile Type obtained in different embodiments；
The optical microphotograph pattern of titanium slag when Fig. 3 is different oxidizing temperatures；
Fig. 4 is influence of the oxidizing temperature to rutile degree of enrichment and crystallite dimension；
Fig. 5 is optical microphotograph pattern of the titanium slag under different oxidization times；
Fig. 6 is influence of the oxidization time to rutile degree of enrichment and crystallite dimension；
Fig. 7 is different rate of temperature fall rutile crystal patterns (× 200)；
Fig. 8 is influence of the rate of temperature fall to rutile degree of enrichment and crystallite dimension；
Fig. 9 is titanium slag back scattering microstructure before modification；
Figure 10 is the XRD diffracting spectrums of titanium slag before modification；
Figure 11 is titanium slag back scattering microstructure after modification；
Figure 12 is the XRD diffracting spectrums of titanium slag after modification.
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 enrichment of the modifying agent and synthetic rutile provided in an embodiment of the present invention for producing rutile using titanium slag
Method is specifically described.
A kind of modifying agent producing rutile using titanium slag provided in an embodiment of the present invention, including silica, and dioxy
The dosage of SiClx is the 8%-15%, preferably 10%-12% of titanium slag dosage.
It should be noted that by being aoxidized to titanium slag, high-temperature heat treatment modification make slag middle or low price titanium (Ti2+, Ti3+) oxidation
For Ti4+, improve TiO in slag2Activity, promote rutile evolution reaction：(TiO2)=TiO2(s) it carries out to the right.Additive is added
SiO2, promote impurity in anosovite phase to enter magma cell, and titanium component enters Rutile Type.Meanwhile modified heat treatment
Rutile crystal can be made to grow up and be roughened again, be detached convenient for subsequent handling.
In addition, inventor has found that silica only contains in modification slag as the control of additive its dosage at 10% or so
The degree of enrichment of Rutile Type and glass phase, Rutile Type can reach 86%.And the used in amounts of silica is controlled certain
In range, the degree of enrichment of Rutile Type is low if the dosage of silica is too low, if the dosage of silica crosses conference dilution titanium
TiO in slag2Grade, while economic benefit also will receive influence.
The embodiment of the present invention additionally provides a kind of enrichment method of synthetic rutile, includes the following steps：
S1, after mixing titanium slag with rutile type titanium white, oxygen-containing gas is passed through under 1500-1700 DEG C of temperature condition
Carry out oxidation processes 6-12min.
It should be noted that rutile type titanium white, which is added, is also known as rutile TiO2, it is the titanium enrichment in follow-up titanium slag
Guiding role is played to Rutile Type.The process of oxidation is that titanium slag is made to aoxidize, and makes Low-valent Titanium (Ti in part in slag2+, Ti3+) oxidation
For Ti4+, the yield for finally obtaining Rutile Type is promoted, while promoting the utilization rate of titanium slag.
It should be pointed out that oxidizing temperature and oxidization time are important parameters in oxidation processes.Oxidizing temperature
Excessively high that rutile crystal can be made coarse, temperature is too low to make crystal development incomplete, and coarse crystal grain is smaller.Inventor's discovery,
When preferable temperature is 1510-1560 DEG C, rutile crystal is coarse in this temperature range and physically well develops, and fine grain is less, base
All it is irregular square crystal in sheet.Rutile crystal is tiny when oxidization time is shorter, is unfavorable for enrichment and separation, oxidization time
Rutile crystal is coarse when long；Inventor has found that Rutile Type mean grain size has increased trend with oxidization time, and with
Oxidization time is advisable for 7-9min, tends towards stability more than the granularity of Rutile Type after this range and the variation of degree of enrichment.
Specifically, the dosage of rutile type titanium white is the 0.1%-2.0%, preferably 0.5%-1.0% of titanium slag dosage.
The dosage of rutile type titanium white mainly plays guiding role to follow-up enrichment process, and dosage should not be excessive.Dosage controls
The degree of enrichment of Rutile Type can be made to reach higher level within the scope of 0.5%-1.0%.
Specifically, oxygen-containing gas can be mixed gas, including oxygen and some be not involved in the gas such as nitrogen of reaction,
In oxygen content controlled, the oxygen content in oxygen-containing gas be 30%-60%.Wherein, the excessively high meeting of oxygen content
Make oxidation rate is too fast to be unfavorable for obtaining uniform and high-purity Rutile Type, the content of oxygen is too low to make oxidation rate mistake
Slowly, it is susceptible to the incomplete phenomenon of oxidation, influences the rate of recovery of titanium in titanium slag.
Preferably, during being passed through oxygen-containing gas, control gas flow rate is 1.5-2.5L/min.Mixed gas is led to
Enter the gas for being on the one hand to provide oxidation process, is on the other hand to play stirring action, the too fast excessively slow influence of flow velocity of gas
It is referred to the influence process of above-mentioned oxygen content, in addition, the flow velocity of gas is also easy to influence the uniformity of material mixing slowly excessively,
It is susceptible to the uneven phenomenon of material mixing, and causes oxidation incomplete.
Further, the reactor equipped with titanium slag and crystal seed is first warming up to 1500-1700 DEG C before being passed through oxygen-containing gas
Afterwards, 20-40min is kept the temperature.First passing through the soak of a period of time before the oxidation makes titanium slag melt, and is conducive in follow-up golden red
The enrichment process of stone phase is that silica is added in the state that titanium slag is in homogeneous liquid phase to be modified, and anosovite is made to be oxidized to
Rutile, allows overwhelming majority TiO in slag2Under the driving of chemical potential gradient, selectively enrichment is Rutile Type, and is realized
Selective separation-out and roughening.
S2, modifying agent is added after the oxidising treat-ment, then starts to cool down.
Specifically, modifying agent includes silica, and the 8%-15% that the dosage of silica is titanium slag dosage, preferably
10%-12%.Additive SiO is added2, promote impurity in anosovite phase to enter magma cell, and titanium component enters golden red
Shi Xiang.Meanwhile modified heat treatment can make rutile crystal grow up and be roughened again, be detached convenient for subsequent handling.The use of silica
Amount needs to control in a certain range, and inventor has found that the dosage when silica is 10%-12%, only contains gold in modified slag
Red stone phase and glass phase, the degree of enrichment of Rutile Type reach 86%.
Specifically, it is to be first down to 700-900 DEG C with the rate of temperature fall of 1-3 DEG C/min in temperature-fall period, then comes out of the stove again
It is air-cooled.It is with 1500-1700 DEG C in temperature-fall period for initial temperature, first carries out being cooled to 700- with lower rate of temperature fall
It 900 DEG C, then comes out of the stove again air-cooled.It is initial to be cooled down compared with low rate during, rate of temperature fall is controlled,
Rate of temperature fall is comparatively fast unfavorable for crystal and grows up, and carrying out cooling with slower rate of temperature fall is conducive to crystal and fully grows up, and conveniently
Separation.
In other embodiments, modifying agent further includes manganese oxide and chromium oxide, silica, manganese oxide and chromium oxide matter
Amount is than being 3-5:1-2:1, preferably 3.5-4.5:1.5-2.5:1.The melt that is added to reduce of manganese oxide and chromium oxide glues
Degree improves mass transfer condition, and Rutile Type is promoted to grow up, be roughened, and dosage will be less than the dosage of silica.
In addition, can be detached after Rutile Type is selectively grown up, is roughened：Titanium component is selectively enriched in gold
Red stone phase and Rutile Type are selectively grown up, and treated cools down crust block, and gravity treatment or Chemical Decomposition side are used after broken, levigate
Method separates Rutile Type in crust block, obtains high-grade TiO2Synthetic rutile.It is existing skill that this, which is partially separated process,
Art is not done excessively repeat in embodiments of the present invention.
The feature and performance of the present invention are described in further detail with reference to embodiments.
Embodiment 1
Present embodiments provide a kind of enrichment method of synthetic rutile comprising following steps：
By 500g titanium slags and 0.5g rutile type titanium whites by crucible is packed into after evenly mixing, it is placed in MoSi2In stove, by slag
Sample is warming up to 1500 DEG C and keeping the temperature 20min makes slag specimen melt；Rate with gas flow rate for 1.5L/min is passed through oxygen-containing into stove
Gas aoxidizes 6min, and oxygen content is 30% in oxygen-containing gas；Modifying agent silica is added after oxidation, silica
Dosage is the 8% of slag specimen dosage, then carries out being cooled to 700 DEG C with the rate of temperature fall of 1 DEG C/min, then come out of the stove air-cooled.
Embodiment 2
Present embodiments provide a kind of enrichment method of synthetic rutile comprising following steps：
By 500g titanium slags and 2.5g rutile type titanium whites by crucible is packed into after evenly mixing, it is placed in MoSi2In stove, by slag
Sample is warming up to 1700 DEG C and keeping the temperature 40min makes slag specimen melt；Rate with gas flow rate for 2.5L/min is passed through oxygen-containing into stove
Gas aoxidizes 12min, and oxygen content is 60% in oxygen-containing gas；Modifying agent silica, silica are added after oxidation
Dosage be slag specimen dosage 15%, then carry out being cooled to 900 DEG C with the rate of temperature fall of 3 DEG C/min, then come out of the stove air-cooled.
Embodiment 3
Present embodiments provide a kind of enrichment method of synthetic rutile comprising following steps：
By 500g titanium slags and 10g rutile type titanium whites by crucible is packed into after evenly mixing, it is placed in MoSi2In stove, by slag
Sample is warming up to 1530 DEG C and keeping the temperature 30min makes slag specimen melt；Rate with gas flow rate for 2L/min is passed through oxygenous into stove
Body aoxidizes 7min, and oxygen content is 40% in oxygen-containing gas；Modifying agent silica, the use of silica are added after oxidation
Amount is the 10% of slag specimen dosage, then carries out being cooled to 800 DEG C with the rate of temperature fall of 2 DEG C/min, then come out of the stove air-cooled.
Embodiment 4
Present embodiments provide a kind of enrichment method of synthetic rutile comprising following steps：
By 500g titanium slags and 8g rutile type titanium whites by crucible is packed into after evenly mixing, it is placed in MoSi2In stove, by slag specimen
It is warming up to 1560 DEG C and keeping the temperature 30min makes slag specimen melt；Oxygen-containing gas is passed through into stove for the rate of 2L/min with gas flow rate
9min is aoxidized, oxygen content is 40% in oxygen-containing gas；Modifying agent silica, the dosage of silica are added after oxidation
It is the 12% of slag specimen dosage, then carries out being cooled to 800 DEG C with the rate of temperature fall of 2 DEG C/min, then come out of the stove air-cooled.
Embodiment 5
Present embodiments provide a kind of enrichment method of synthetic rutile comprising following steps：
By 500g titanium slags and 5g rutile type titanium whites by crucible is packed into after evenly mixing, it is placed in MoSi2In stove, by slag specimen
It is warming up to 1510 DEG C and keeping the temperature 30min makes slag specimen melt；Oxygen-containing gas is passed through into stove for the rate of 2L/min with gas flow rate
8min is aoxidized, oxygen content is 40% in oxygen-containing gas；Modifying agent silica, the dosage of silica are added after oxidation
It is the 10% of slag specimen dosage, then carries out being cooled to 800 DEG C with the rate of temperature fall of 2 DEG C/min, then come out of the stove air-cooled.
Embodiment 6
It is roughly the same with embodiment 5, the difference is that, silica content is the 2% of slag specimen dosage.
Embodiment 7
It is roughly the same with embodiment 5, the difference is that, silica content is the 4% of slag specimen dosage.
Embodiment 8
It is roughly the same with embodiment 5, the difference is that, silica content is the 6% of slag specimen dosage.
Embodiment 9
It is roughly the same with embodiment 5, the difference is that, silica content is the 8% of slag specimen dosage.
Embodiment 10
It is roughly the same with embodiment 5, the difference is that, oxidizing temperature is 1520 DEG C.
Embodiment 11
It is roughly the same with embodiment 5, the difference is that, oxidizing temperature is 1530 DEG C.
Embodiment 12
It is roughly the same with embodiment 5, the difference is that, oxidizing temperature is 1540 DEG C.
Embodiment 13
It is roughly the same with embodiment 5, the difference is that, oxidizing temperature is 1550 DEG C.
Embodiment 14
It is roughly the same with embodiment 5, the difference is that, oxidization time 2min.
Embodiment 15
It is roughly the same with embodiment 5, the difference is that, oxidization time 4min.
Embodiment 16
It is roughly the same with embodiment 5, the difference is that, oxidization time 6min.
Embodiment 17
It is roughly the same with embodiment 5, the difference is that, oxidization time 10min.
Embodiment 18
It is roughly the same with embodiment 5, the difference is that, rate of temperature fall is 4 DEG C/min.
Embodiment 19
It is roughly the same with embodiment 5, the difference is that, rate of temperature fall is 6 DEG C/min.
Embodiment 20
It is roughly the same with embodiment 5, the difference is that, rate of temperature fall is 8 DEG C/min.
Embodiment 21
It is roughly the same with embodiment 5, the difference is that, rate of temperature fall is 10 DEG C/min.
Embodiment 22
It is roughly the same with embodiment 5, the difference is that, modifying agent further includes manganese oxide and chromium oxide, and silica,
The mass ratio of manganese oxide and chromium oxide is 3:1:1.
Embodiment 23
It is roughly the same with embodiment 5, the difference is that, modifying agent further includes manganese oxide and chromium oxide, and silica,
The mass ratio of manganese oxide and chromium oxide is 5:2:1.
Test example 1
The variation of high-titanium blast furnace slag and component after oxidation in testing example 5, wherein it is artificial that titanium slag liquid phase is modified production
The raw material that rutile uses is the common acid-dissolved titanium slag for climbing western ilmenite production, and slag specimen ingredient is shown in Table 1, additive SiO2To divide
Analyse pure reagent.
The primary chemical composition (quality %) of 1 high titanium slag of table
X-ray diffracting spectrum such as Fig. 1 institutes of unoxidized acid-dissolved titanium slag raw material and 1530 DEG C of high-temperature oxydation product
Show.
Represents Rutile Type in Fig. 1, ◆ magnesium anosovite is represented, × pseudobrookite, ◇ represents Fe, and ■ represents Fe2O3,
● anatase, ▲ represent FeO.As shown in Figure 1, after peroxidating in addition to Rutile Type, remaining each phase (anosovite, iron plate titanium
Mine, FeO and Fe2O3) disappeared, Rutile Type diffraction peak is stronger.
Test example 2
Influence of the dosage of modifying agent silica to selective enrichment in testing example 5-9, using conventional method
The degree of enrichment result for testing the Rutile Type obtained in different embodiments is shown in Fig. 2.
As shown in Figure 2, with SiO2The degree of enrichment of the increase of addition, Rutile Type accordingly increases.Work as SiO2Addition is big
In 8%, degree of enrichment is more than 80%, but excessively high SiO2Addition will dilute TiO in titanium slag2Grade, while economic benefit also can be by
To influence, therefore select SiO2Addition is advisable for 10%.
Test example 3
Influence of the oxidization time to rutile crystalline behavior in testing example 5 and embodiment 10-13, as a result such as Fig. 3 and
Fig. 4.The optical microphotograph pattern of slag specimen when Fig. 3 is different oxidizing temperatures, Fig. 4 are oxidizing temperature to rutile degree of enrichment and crystal grain ruler
Very little influence.
From the figure 3, it may be seen that oxidizing temperature high-rutile crystal is coarse, rutile crystal is tiny at 1510 DEG C, and crystal development is not
Completely, coarse crystal grain is less (Fig. 3 a).Rutile crystal is coarse at 1550 DEG C, physically well develops, and fine grain is less.It is substantially all
It is irregular square crystal (Fig. 3 b).
As shown in Figure 4, at 1510 DEG C, oxidizing temperature is relatively low, and there is no complete oxidations for original anosovite crystal, but
It is cracked into smaller crystal relic, thus influences the precipitation of rutile crystal.With the raising of oxidizing temperature, oxidation rate adds
Soon, rutile is precipitated accelerates with coarsening rate.After fusion temperature is more than 1530 DEG C, the crystallization content variation of rutile eases up, therefore
Being 1530 DEG C with oxidizing temperature is advisable.
Test example 4
Influence of the oxidization time to rutile crystalline in testing example 5 and embodiment 14-17, is as a result shown in Fig. 5 and Fig. 6.
Fig. 5 is optical microphotograph pattern of the slag specimen under different oxidization times, and Fig. 6 is oxidization time to rutile degree of enrichment and crystallite dimension
Influence.
As shown in Figure 5, rutile crystal is tiny when oxidization time is 2min, rutile crystal when oxidization time is 10min
It is coarse.I.e. Rutile Type mean grain size has the tendency that growing up with the extension of oxidization time.It will be appreciated from fig. 6 that with soaking time
Extend, Rutile Type mean grain size increases with degree of enrichment.When oxidization time is more than 8min, variation tends towards stability, therefore when oxidation
Between be selected as 8min and be advisable.
Test example 5
Influence of the rate of temperature fall to rutile crystalline in testing example 5 and embodiment 18-21, is as a result shown in Fig. 7 and Fig. 8.
Fig. 7 is different rate of temperature fall rutile crystal patterns (× 200), and Fig. 8 is rate of temperature fall to rutile degree of enrichment and crystallite dimension
Influence.
As shown in Figure 7, rutile crystal is coarse when 2 DEG C/min Slow coolings, for coarse blocky square crystal.10℃/min
When rutile crystal it is tiny, have part elongated.As shown in Figure 8, the average grain size of rutile and rutile degree of enrichment
Reduce with the increase of rate of temperature fall, rate of temperature fall, which is selected as 2 DEG C/min, to be advisable.
Test example 6
Process mineralogy research is carried out to the slag charge in embodiment 5 before modified, tests acid-soluble titanium before modification respectively
As a result the mine phase composition of slag and content are shown in Fig. 9, Figure 10 and table 2.Fig. 9 is high titanium slag back scattering microstructure before modification
(Sp1：Anosovite, Sp2：Glass phase), Figure 10 is the XRD diffracting spectrums of high titanium slag before modification.
The EDAX analysis results (quality %) of the main object phase of acid-dissolved titanium slag before 2 modification of table
Compare Fig. 9, Figure 10 with table 2 it is found that essential mineral is mutually anosovite, silicate glass in high titanium slag before modification
Deng.Before modification in high titanium slag the characteristics of each essential mineral phase：
(1) anosovite：Main titaniferous object is mutually anosovite in former high titanium slag, and crystallizes object phase earlier, nonmagnetic
Or weak magnetic, matter is crisp, and content of titanium dioxide is generally less than 85%.
(2) ulvite solid solution：It is to belong to equiax crystal with the solid solution that ulvite (2FeOTiO2) is lattice
System, opaque, weak magnetic.
(3) magma cell：It is main silicate mineral, organizes the substrate mineral facies of slagging, other mines is mutually more uniform
Wherein, 8~15% titanium dioxide is distributed in magma cell to the embedding cloth in ground.
Test example 7
(1) process mineralogy research is carried out to slag charge modified in embodiment 5, it is acid-soluble before test modification respectively
The mine phase composition of titanium slag and content, the result is shown in Figure 11, Figure 12 and table 3.Figure 11 is the micro- shape of high titanium slag back scattering after modification
Looks (Sp1：Anosovite, Sp2：Glass phase), Figure 12 is the XRD diffracting spectrums of high titanium slag after modification.
The EDAX analysis results (quality %) of the main object phase of high titanium slag after 3 modification of table
By Figure 11, Figure 12 and table 3 it is found that the titanium in treated high titanium slag is mainly enriched in Rutile Type (Sp1), and
Other ingredients are in glass matrix phase (Sp2).Titanium elements are up to 69.590% in Sp1 phases, and titanium elements only have in Sp2 phases
3.621%, it is mainly enriched in Rutile Type (Sp1) after the titanium component in former slag is oxidized and additive treating, is realized
Selective enrichment.
(2) 4, modified slag mine the results are shown in Table using the chemical composition of modified slag specimen in conventional method testing example 5
Object composition the results are shown in Table 5 and rutile object Lens capsule the results are shown in Table 6.
4 chemical analysis results (quality %) of table
As shown in Table 4, with former slag phase ratio, it is modified TiO in slag specimen2Content declines, and reason is：Additive SiO2Addition
Reduce TiO in slag specimen2Content, in addition, since acid-dissolved titanium slag aggressivity is extremely strong, it is existing that there are larger mass transfers between crucible
As, therefore, TiO in modified slag specimen2Content declines.
Table 5 is modified titanium slag material phase analysis result
As shown in Table 5, the titanium in ore is existed with independent rutile form, still there is fraction titanium dispersed silicon
(TiO in silicate glass phase2＜ 3.7%).
The grain class distribution of 6 rutile of table
As shown in Table 6, rutile disseminated grain size is special thin and uneven, and+50 μm of grades only account for the 38.43% of rutile, greatly
40~50 μm of part disseminated grain size.
By this test example it is found that (1) modified slag specimen chemical composition and mineral composition are simple, only Rutile Type and vitreum
Phase two-phase, TiO2Content is 68.21%, and it mainly exists with independent rutile form；Alundum (Al2O3), oxygen in modified slag specimen
Change the impurity such as calcium, iron oxide and magnesia to be mainly gathered in vitreum phase, direct acidleach, alkali leaching are all not easy to remove.(2) golden
Red stone disseminated grain size is uneven, wherein+50 μm of grades only account for 38.43%, the disseminated grain size of most of rutile is less than 50 μm, spy
It is not that 40~50 μm of grade occupation rates are up to 35.12%.In addition, -40 μm of grade occupation rates 27.45% this will directly affect gold
Red stone mineral processing index.Therefore, for the abundant monomer dissociation of rutile, needs to consider mog carefully, be crushed in order to avoid crossing,
Multistage grinding should be used, is repeatedly sieved.
In conclusion the present invention also provides a kind of enrichment methods of synthetic rutile, using titanium slag as raw material, first by titanium
Slag is mixed with rutile type titanium white, and rutile type titanium white plays guiding role, then in 1500-1700 DEG C of temperature condition
Under be passed through oxygen-containing gas and aoxidized, convert lower valency titanium to titanic, then dropped under the action of silica modified dose
Temperature crystallization is precipitated, and obtains the Rutile Type of high degree of enrichment.Therefore, the enrichment method of synthetic rutile provided by the invention can fill
The titanium recycled in titanium slag, recovery method energy conservation and environmental protection is divided not to generate the high impurity of environmental pollution degree, and the purity of product
Height has good market application prospect.
A kind of modifying agent producing rutile using titanium slag provided by the invention, during the utilization of titanium slag, titanium dioxide
Silica modifier can be such that the titanium component in titanium slag is enriched in Rutile Type, and impurity element releases to form silicon from anosovite
Silicate glass phase；It is modified in slag when the dosage of silica is controlled 10% or so and only contains Rutile Type and glass phase, gold
The degree of enrichment of red stone phase reaches 86%.
A kind of crystal seed producing rutile using titanium slag provided by the invention, can produce the crystalline substance of rutile as titanium slag
Kind, obtain the rutile of high degree of enrichment.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.The reality of the present invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of the selected implementation of the present invention
Example.Based on the embodiments of the present invention, those of ordinary skill in the art are obtained without creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (10)
1. a kind of crystal seed producing rutile using titanium slag, which is characterized in that including the crystal seed that titanium dioxide is enriched with as rutile,
Preferably, the titanium dioxide is rutile type titanium white, and the titanium dioxide dosage is the 0.1%-2.0% of the titanium slag, preferably
For 0.5%-1.0%.
2. a kind of modifying agent producing rutile using titanium slag, which is characterized in that including silica, and the silica
Dosage is the 8%-15%, preferably 10%-12% of the titanium slag dosage.
3. a kind of enrichment method of synthetic rutile, which is characterized in that include the following steps：
After titanium slag is mixed with titanium dioxide crystal seed heat melting, be passed through under 1500-1700 DEG C of temperature condition oxygen-containing gas into
Row oxidation processes 6-12min；Modifying agent is added after the oxidising treat-ment, then starts to cool down；Wherein, the modifying agent includes dioxy
SiClx, and the 8%-15%, preferably 10%-12% that the dosage of the silica is the titanium slag dosage；
Preferably, the titanium dioxide is rutile type titanium white, and the titanium dioxide dosage is the 0.1%-2.0% of the titanium slag,
Preferably 0.5%-1.0%.
4. the enrichment method of synthetic rutile according to claim 2, which is characterized in that be first with 1- in temperature-fall period
The rate of temperature fall of 3 DEG C/min is down to 700-900 DEG C, then comes out of the stove again air-cooled.
5. the enrichment method of synthetic rutile according to claim 2, which is characterized in that first will before being passed through oxygen-containing gas
After reactor equipped with titanium slag and crystal seed is warming up to 1500-1700 DEG C, 20-40min is kept the temperature.
6. the enrichment method of synthetic rutile according to claim 5, which is characterized in that in the process for being passed through oxygen-containing gas
In, control gas flow rate is 1.5-2.5L/min.
7. the enrichment method of synthetic rutile according to claim 2, which is characterized in that the oxidization time is 7-
9min。
8. the enrichment method of synthetic rutile according to claim 7, which is characterized in that the oxygen in the oxygen-containing gas
Content is 30%-60%.
9. the enrichment method of synthetic rutile according to claim 2, which is characterized in that the modifying agent further includes oxidation
Manganese and chromium oxide.
10. the enrichment method of synthetic rutile according to claim 9, which is characterized in that described in the modifying agent
The mass ratio of silica, the manganese oxide and the chromium oxide is 3-5:1-2:1.
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|---|---|---|---|---|
| CN1594103A (en) * | 2004-07-14 | 2005-03-16 | 湖南永利化工股份有限公司 | Process for preparing crystal seed used for rutile type titanium dioxide production |
| CN1919740A (en) * | 2006-07-18 | 2007-02-28 | 隋智通 | Method of producing synthetic rutile utilizing high-titanium slag |
| 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 |
| JP6468457B2 (en) * | 2014-07-03 | 2019-02-13 | Dic株式会社 | Titanium oxide particles and method for producing the same |
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2018
- 2018-04-20 CN CN201810360367.2A patent/CN108483488A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1594103A (en) * | 2004-07-14 | 2005-03-16 | 湖南永利化工股份有限公司 | Process for preparing crystal seed used for rutile type titanium dioxide production |
| CN1919740A (en) * | 2006-07-18 | 2007-02-28 | 隋智通 | Method of producing synthetic rutile utilizing high-titanium slag |
| 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 |
| JP6468457B2 (en) * | 2014-07-03 | 2019-02-13 | Dic株式会社 | Titanium oxide particles and method for producing the same |
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