CN103201221B - Titania method A improved - Google Patents
Titania method A improved Download PDFInfo
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- CN103201221B CN103201221B CN201180027805.XA CN201180027805A CN103201221B CN 103201221 B CN103201221 B CN 103201221B CN 201180027805 A CN201180027805 A CN 201180027805A CN 103201221 B CN103201221 B CN 103201221B
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- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1204—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 preliminary treatment of ores or scrap to eliminate non- titanium constituents, e.g. iron, without attacking the titanium constituent
- C22B34/1209—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 preliminary treatment of ores or scrap to eliminate non- titanium constituents, e.g. iron, without attacking the titanium constituent by dry processes, e.g. with selective chlorination of iron or with formation of a titanium bearing slag
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
Abstract
The method from the ilmenite being unsuitable for standard Becher method, titanium reclaimed as titania, comprise the following steps: in the presence of carbonaceous reducing agent, the ilmenite being unsuitable for standard Becher method is processed in reducing atmosphere, thus ilmenite is converted into the ilmenite after reduction, wherein the iron oxides in ilmenite has been reduced into metallic iron, and is separated by described metallic iron thus obtain titania product.Described process to ilmenite is at high temperature carried out, and described high temperature is less than as the TiO of titania product2Content is the highest but there is no temperature when reoxidizing of metallic iron.Described carbonaceous reducing agent comprises the coal selected due to gasification activity, and described gasification activity makes the rate of reduction of iron oxides and titanium material improve, and the most at least partly compensate for TiO in the titania product caused by relatively low described high temperature2The reduction of content, and have effectively achieved 90% or higher TiO in described titania product2Content.
Description
Invention field
The present invention relates to be reclaimed as titania by titanium from the Ore of titaniferous, especially from primary ilmenite, hydridization ilmenite and other ferrum containing higher proportion or problematic impurities or containing the ilmenite of the titanium of minor proportion, titanium is reclaimed as titania.
Background of invention
Becher reducing process is the standard method reclaimed by titanium dioxide from the ilmenite composition of ore deposit, Western Australia sand bed, in this method, in the atmosphere of reproducibility and in the presence of coal, by ilmenite at revolution kiln roasting, so that the iron oxides in ilmenite is reduced to metallic iron, then separate to obtain the product of referred to as titania, TiO in this product by metallic iron by aqueous phase oxidation (aqueousoxidation)2Content be usually 90% or more.Titania is to be further processed into Chinese white or the raw material of other application.These are further processed TiO2The minimum of content is very sensitive, and the yield of Becher reducing process depends on again the ilmenite charging specification that comparison is strict, such as, in Western Australia, iron content is measured as FeO < 12%.In a practical situation, the raw material of Becher method is limited to secondary ilmenite (secondaryilmenites), also referred to as alteration ilmenite (alteredilmenites) or alteration ilmenite (weatheredilmenites) by this.
Primary ilmenite contains higher iron content, is not suitable for Becher method, but in Western Australia, the so-called sulfate ilmenite sulfate process selected as the election of 16% < FeO < 24% prepares TiO2The raw material of approach is commercially valuable.Ilmenite between Becher method and sulfate process is referred to as hydridization ilmenite, and i.e. 12% < FeO < 16%, it does not has commercial use.
In the ilmenite raw material of Becher method, the strict upper bound of FeO content is related to prevent reoxidizing of in reduction process ferrum.Although causing situation about reoxidizing to be difficult to measure and control in stove, but it is known that due to the result risk of higher iron content and reunion or sintering and in bulk, reoxidizing of Primary ilmenite is more notable.It is known that, susceptible reoxidizing (thus tackling the formation of reunion) can be tackled by the operation temperature reducing stove, such as, the temperature range about 1100-1150 DEG C of representative Becher method is reduced to about the 1000-1025 DEG C formation that can make reunion/sintering and be reduced to acceptable level.Problem be the speed of production of the titania thereby resulted in be uneconomic.
In the area that secondary ilmenite resource is reducing, the restricted ilmenite specification for Becher method becomes the most urgent problem.From the viewpoint of the owner of these resources, the resource of the hydridization ilmenite containing certain limit FeO content and sulfate ilmenite and is persistently had the hope obtaining bigger commercial return.
At other, there is the province of ilmenite, MurrayBasin and NewSouthWales of such as Victoria, owing to the ratio of the titanium that the content height of unfavorable impurity, the especially content of magnesium and chromium are high and thus cause is relatively low, therefore these existing ilmenites are not suitable as the raw material of Becher method.Such as, ilmenite secondary for Western Australia is FeO < 12%, 57% < TiO for the standard feed specification of Becher method2<65%.TiO in the ilmenite of MurrayBasin2Content be usually about 54-56%, the content of magnesium is usually 1.5-2.5%, and the content of chromium is about 1%.
Therefore, it is an object of the invention to provide from Primary ilmenite, hydridization ilmenite and containing the ferrum of higher proportion or problematic impurities or containing the commercially useful method reclaiming titanium dioxide the ilmenite of the titanium of minor proportion.These ilmenites be not collectively referred to herein as suitable for the ilmenite of standard Becher method.
Using any prior art in this specification as with reference to not being or be not construed as recognizing or implying in any form, the prior art constitutes the part of the common knowledge in other jurisdiction of courts Australian or any or the prior art can be reasonably expected that by those skilled in the art to become and be determined, is understood and is considered as relevant.
Summary of the invention
For FeO>for the Primary ilmenite of 16%, have been found that the speed formed by the sintering reoxidized at 1100 DEG C may be up to 6 times of the ilmenite of FeO<12%, and this getting off of temperature that only can be used by the temperature of reduction treatment is greatly reduced usual Becher method prevents.It has also been found that > the acceptable level titania of 93% still can produce at a temperature of such as 1025 DEG C, must be low but the throughput rate of titania is unacceptable.According to the present invention, have surprisingly found that, make Primary ilmenite or hydridization ilmenite for Becher method this unacceptable result uneconomic, can have the coal reductant of gasification activity by use compensate and really overcome, the gasification activity of described coal reductant makes the rate of reduction of iron oxides and titanium material improve.
The invention provides the method reclaimed by titanium from the ilmenite being unsuitable for standard Becher method as titania, comprise the following steps: in the presence of carbonaceous reducing agent, in reducing atmosphere, process the ilmenite being unsuitable for standard Becher method, thus ilmenite is converted into the ilmenite after reduction, wherein the iron oxides in ilmenite has been reduced into metallic iron, and is separated by described metallic iron thus obtain titania product.The method is characterized in that, the above-mentioned process to ilmenite is at high temperature carried out, and described high temperature is less than as the TiO of titania product2Content is the highest but there is no temperature when reoxidizing of metallic iron, and the method is characterized in that, described carbonaceous reducing agent comprises the coal selected owing to having gasification activity, described gasification activity makes the rate of reduction of iron oxides and titanium material improve, and the most at least partly compensate for TiO in the titania product caused by relatively low described high temperature2The reduction of content, and effectively achieved 90% or higher TiO in described titania product2Content, preferably at least 93%.
Possible coal gasification reactivity is the most sufficiently high to realize described compensation, but the high level of gasification activity is probably inadequate.Coal gasification reactivity can be higher, and meaning that in this specification context will be apparently higher than the meansigma methods of all coals.It practice, this means the gasification activity higher-end close to the gasification activity scope being commonly found in coal.Gasification activity is preferably more than 0.005g-g/min at 850 DEG C, and more preferably more than 0.01g-g/min at 850 DEG C, the two value is all for coal tar at atmosheric pressure.Alternatively or other gasification activity is preferably at least twice of representative Collie coal, at least three times of the most representative Collie coal.
The high temperature of described process is preferably less than 1050 DEG C, more preferably 975-1035 DEG C, most preferably 1000-1030 DEG C.
The level of the calcium of ion exchange is a known index of higher coal gasification reaction, although other impurity elements are considered as to play similar effect.Then, selected coal preferably has the inorganic elements of the ion exchange of the sufficiently high impurity level to improve coal gasification speed, thus improves the reducing condition in method and therefore improve iron oxides and the rate of reduction of titanium material.Such element can include alkali earth metal such as calcium and magnesium or alkali metal such as sodium or ferrum.The coal of calcium having been found that the ion exchange containing higher level is useful especially.
The ratio measuring the element being usable acid extraction of the inorganic elements of the most high-caliber ion exchange: this ratio is desirably greater than 50%, more preferably greater than 70%, most preferably more than 80%.Usefully, the amount of at least one such inorganic elements at least 0.2%db in terms of dry coal exists.
Although coal can be the coal of any grade, including bituminous coal, suitable coal includes ub-bituminous coal or brown coal, and in selected coal, the total content of water is 5-40%, or intrinsic water content is 5-25%, and intrinsic water content is most preferably about 20% or less.The content of volatile substances is preferably greater than 30%, and most preferably greater than 40%.The content of ash is preferably less than 10%, and most preferably less than 5%.
The content of final hydrogen in terms of dry ash preferably greater than 4% in coal.Final carbon content is preferably greater than 65%.The melt temperature of ash can be more than 1100 DEG C (more preferably at least 1150 DEG C) in terms of initial deformation temperature (I.D.T.), can be more than 1200 DEG C (more preferably at least 1250 DEG C) in terms of hemispherical fusion temperature (H.T.).
Preferably, before being transported to described process step, charcoal is mixed with ilmenite.Have been found that the existence of the charcoal mixed with ilmenite further helps in reduce to be produced by reoxidizing to reunite or the speed of sintering.
Preferably, the sulfur content of coal is less than 1%w/w, more preferably less than 0.5%w/w, more preferably less than 0.2%w/w.Preferably, within the most of the time of described process, there is not extra sulfur.Have been found that, the sulfur higher than these preferred levels above-mentioned contained in coal is (such as, by providing low-sulfur coal and the blend of sulphur coal component) or the sulfur that existed by extra sulfur, all negatively affecting the reactivity of ilmenite, iron oxides (is converted to the speed of metallic iron) in reduction treatment step by the most metallized speed.
Therefore, if in order to improve TiO in the titania product of the method further2Content, then wish to carry in ilmenite sulfur in described process step process, such as, in order to make a return journey demanganization impurity with the form of Manganese monosulfide., such conveying only later stage during reduction treatment is carried out.Such as, only last 3 hours in 9 hours process time are carried out.
Iron content in ilmenite, represents with FeO, can be FeO>12%, such as 12%<FeO<30%.
Preferably, process free oxygen content in atmosphere and be not more than 2.5%, and preferably smaller than 2%, more preferably less than 1%.
Preferably, the process at high temperature in reducing atmosphere is to carry out in the revolving burner tilted, and it is that this stove is typically used in Becher method.Be referred to as the ilmenite of reduction from the low side recycled materials of stove, it is metallic iron and the mixture containing balance iron with the titanium dioxide of other impurity.The ilmenite of this reduction is cooled down to prevent reoxidizing and carrying out separating step subsequently of metallic iron.
Ferrum removal step can be any applicable separation method used in Becher reducing process.Usual such method is wet oxidation step, wherein in the dilute aqueous solution of ammonium chloride catalyst, is aoxidized by metallic iron or gets rusty for magnetic iron ore, bloodstone or lepidocrocite.
The final stage that ferrum and mangana matter are removed further may be needed acidleach or pickling, generally use sulphuric acid (such as, the twice of intensity in 1 ~ 2M, at least standard method).
Should be understood that, the method of the present invention is applicable to Primary ilmenite and hydridization ilmenite (depending on concrete area) and other are not suitable for the ilmenite of standard Becher method, such as, there is relatively low Ti content (such as, 54-56%) and the MurrayBasin ilmenite of higher impurities (magnesium of especially 1.5 ~ 2.5%, the chromium of 1%).
Embodiment
The simple piece sample using some Primary ilmenites being selected to have a series of FeO content carries out a series of test.These ilmenites are YoganupExtended, Wagerup, Cloverdale and Waroona ilmenite in the not homology place of production coming from Western Australia.Selecting YoganupExtended ilmenite to be because its FeO content high (27%), this will represent situation worst in sintering and reduction test result.Other three kinds of ilmenites have the FeO content in the range of above-mentioned sulfate ilmenite.
In order to tentatively test the impact of temperature, under the reduction temperature of 1100 DEG C of standard, utilize Gollie coal by YoganupExtended Primary ilmenite and two large sample reduction of secondary standard Capel ilmenite (FeO12%).Table 1 lists the test result of selected 5 kind ilmenite.The sintering minimum analyzing display Primary ilmenite in preliminary reduction process to the ilmenite (RI-is at the product of the pre-treatment separating metallic iron) of ilmenite and reduction.
In order to set up the temperature impact on sintering, when making RI sample stand different temperature and oxygen concentration, hold it in stove simultaneously.RI sample is placed on platinum crucible and is exposed to that there is 1.2%O2,2.46%O2And 5.3%O2Oxygen and the mixture of nitrogen.Test at 1000 DEG C, 1050 DEG C, 1100 DEG C and 1150 DEG C.By the original RI of mensuration with after 1 minute, from platinum ware, the size of the product of removing measures the generation of sintering.106 μm to 10 kinds of standard aperture granularities of 1mm are used tentatively to screen.Its size results analysis shows that the sintering that the amount of+250 μm and+1mm material is measured when increasing is best.Based on this reason, test afterwards only select 250 μm and 1mm screen.
Sintering is also worked by the existence of charcoal, because it providing against the protection reoxidized.Owing to stove can have separation coal and the district of RI, therefore determine to test the degree of sintering in the case of charcoal exists and be non-existent.
With reference to the sample that ilmenite is 14%FeO of charging, it is selected to form the basis of contrast.The ilmenite of reference represents the highest FeO level, and it has been smoothly through the SR stove processing on side.The result of the ilmenite of reference sets the benchmark of the maximum receivable level of sintering and in order to realize identical sintering level needs how much to reduce reduction temperature.
Table 2 shows the sintering degree after being exposed to the oxygen/nitrogen mixture 1 minute of 5.3% at a temperature of 1000 DEG C, 1050 DEG C, 1100 DEG C and 1150 DEG C.The measurement size of RI and ilmenite is also given for reference.
Data in table 2 are also drawn in FIG.Following observation conclusion can be drawn according to the liter high-temperature in the presence of excess oxygen:
Sintering degree increases along with the rising of temperature.This is proved by the minimizing of the amount of the acinous material of a size of 125 to 150 μm.Along with the rising of temperature, the amount of the aggregate in 212 and 250 μ m in size increases more than 1 times.Compared to 2-particle cluster, the amount of the material representing the+1mm size of many particle clusters also has lifting drastically.
The reunion degree (Fig. 2, table 3) of primary (YoganupExtended) ilmenite recording+1mm is 6 times of standard Capel ilmenite.At 1150 DEG C, in Capel ilmenite, the amount of+1mm sintering is 9.9%, and in Primary ilmenite is 67%.
At 1000 DEG C, the sintering degree in Capel ilmenite and Primary ilmenite is all negligible.The degree increase proportional to temperature and time of sintering.When open-assembly time more than 1 minute time, whole sample can be melt into a block.
The amount of+250 μm in RI that is plotted in shows there is individual flex point when about 1050 DEG C to the figure of temperature.When temperature is more than 1000 DEG C, the raising of sintering rate is significant, especially under the higher oxygen concentration of 5.3%.But, in the case of rupturing at the air hose of shell, under most practical situation, most probable oxygen concentration is 1-2%.Under oxygen concentration is about the low concentration of 1-2%, the amount of+250 μm sintering starts to increase at about 1020 DEG C.
Fig. 3 shows under different reduction temperatures, the amount of+250 additional μm sintering formed after 1 minute in the oxygen concentration increased.Can be appreciated that, when oxygen concentration is below 2.5%, when temperature is below 1100 DEG C, there is the reduction of notable speed.
It turned out, if the temperature of stove is 1000 to 1025 DEG C, so reunite and sinter and just can minimize, be respectively adopted Collie coal (Collie coal is commonly used in Western Australia as solid reductant in using the commercial operation of standard Becher method of secondary ilmenite or alteration ferrotianium) and determined that by test the coal with high gasification activity carries out reduction test.Find that this reactivity coal gasification reactivity is about 5 times of Collie coal gasification reactivity.Result is, this reactivity coal can produce reducibility gas (CO, H at lower temperatures with Collie coal facies ratio2Deng), and it is thus regarded that the reduction of ilmenite also can occur at a lower temperature, thus allow to select the operation temperature of reduction furnace is reduced to desired level.
High pressure thermogravimetric analyzer is utilized to measure the gasification (CO of the charcoal sample (200-300 μm) generated by reactive coal and Collie coal2) reactive behavior.For the sample of about 300mg, due to reactionTherefore CO is determined by the speed of sample weight loss2Reactive.Under atmospheric pressure, test under two kinds of temperature conditionss: one be temperature conditions be constant temperature at 850 DEG C, and another kind be temperature conditions is from 700 DEG C, the alternating temperature increased with the speed of 2 DEG C/min.Latter test may determine that the temperature dependency of gasification reaction.
Table 4 gives the relative reactivity of coal.Can be appreciated that, as it has been described above, find that reactive coal gasification activity at 850 DEG C is about 5 times of Collie coal gasification reactivity.
Table 5 gives the elementary analysis of coal.Can be appreciated that, relative to Collie coal, reactive coal has calcium and the magnesium (difference of a whole order of magnitude) of significantly higher level, and it has also been found that such situation in the analysis of respective ash residue.In terms of dry coal, every kind is about 0.2%db.Confirming, calcium, magnesium also have ferrum in reactive coal presented in ion exchanges.This is by showing that Ca, Mg and Fe acid in reactive coal can extract the order of magnitude that level is 85-95%, and the acid that Ca, Mg and Fe are in Collie coal can be extracted level much lower (less than 50%) and be confirmed.It has been found that the existence at calcium, ferrum, sodium and the small amount of magnesium of the exchange of coal intermediate ion improves gasification activity.By improving coal gasification speed, improve the reducing condition in method, thus improve the rate of reduction of iron oxides.
Every kind of ilmenite is all reduced at 1025 DEG C, and this has been observed that it is to sinter desired maximum allowable operating temperature (M.A.O.T.) in test before.The sample extracted in reductive jar at 4.5,5.0,5.6,6.2,6.8,7.4 and 9.0 hours respectively.Each sample is carried out titrimetry and determines the amount forming metallic iron.Table 6 gives the metallization speed of every kind of ilmenite sample.
Table 6 clearly demonstrates the Collie coal facies rate of reduction for reactive coal, i.e. the metallization realizing 95% in the most whole 9 hours of Collie coal, contrast response coal only needs 5.6 hours.The rate of reduction of Cloverdale ilmenite is more faster than other three kinds of sulfate ilmenites, and it is more like with the behavior of the secondary ilmenite of alteration.The time only needing 5.6 hours is achieved that and reduces completely.Cloverdale ilmenite also has the low FeO content of 18.4% and the minimum MnO content of 0.96%.
Table 7 gives the expectation stove through-put rate of different sulfate ilmenite.Reduction baseline shows, compared with representative thruput (typicalthroughputs), about reduces 45% with the capacity of YoganupExtended sulfate ilmenite (27%FeO) of 22.1 ton hour charging Collie coals.In order to the probability of sintering be minimized, all of reduction temperature is decided to be 1025 DEG C.
By contrast, when using reactive coal at 1025 DEG C, the hope through-put rate of YoganupExtended sulfate ilmenite is 31.8 ton hour (reducing 20%)；And when using reactive coal at 1025 DEG C, the hope through-put rate of Cloverdale sulfate ilmenite is 69.9 ton hour (improve 75%).
Fig. 4 figure depicts the desired feed rate shown in table 7, its two kinds of feed rates of display higher than the sulfate ilmenite of the most common feed rate and two kinds of feed rates less than the sulfate ilmenite of the most common feed rate.FeO content in two kinds of sulfate ilmenites that effect is best is minimum, respectively 18.4%(Cloverdale) and 19.1%(Waroona).In the sulfate ilmenite (through-put rate is reduced more than 20%) that effect is worst, the contents level of FeO is respectively 27%(YoganupExtended) and 19.7%(Wagerup).
The sulphuric acid using 2M concentration carries out acidleach to generate the titania (SR) of simulation to the RI sample from sulfate ilmenite reduction.From the point of view of the leaching to YoganupExtended Primary ilmenite before is tested, find that the sulphuric acid of 2M concentration generates optimal SRTiO2Grade.The intensity of 2M is about 2 times of normal concentration (0.5 ~ 1.0M) of sulphuric acid needed for all ferrum in extraction alteration ilmenite completely.
Table 8 gives the test analysis of the titania product obtained.At a temperature of 1025 DEG C, use reactive coal to test from 4 kinds of sulfate ilmenite samples, wherein have 3 kinds to obtain acceptable SRTiO2Grade.At a temperature of 1025 DEG C, due to slower metallization speed and the incomplete metallization at 9 hours ends, occur in that the unacceptable SRTiO from Collie coal (89.61%)2Grade (< 90%TiO2).Although at a temperature of 1100 DEG C, owing to higher metallization speed achieves the TiO that content is 93.3%2Grade, but higher reduction temperature also has higher sintering risk.
At 1025 DEG C, by using reactive coal from Cloverdale(95.12%) and YoganupExtended(93.00%) Primary ilmenite has obtained acceptable SRTiO2Grade.At 1025 DEG C, by using reactive coal to be can accept from Waroona sulfate ilmenite but SR grade (92.08%) below specification.
Unacceptable SRTiO has been obtained from Wagerup sulfate ilmenite2Grade (88.67%), this is also that in four kinds of sulfate ilmenites, rate of reduction is the slowest.The 96.6%(table 6 lower than 98%) overall total metallization completion rate obtained 8.76% remaining SR iron level.
Fig. 5 shows under similar conditions, use Collie coal and reactive coal reduce in stove respectively Primary ilmenite time iron oxides (being measured by the generation of metallic iron) and the rate of reduction of titanium material.The test of used Primary ilmenite is given below figure.
As used herein, except context additionally needs, term " includes (comprise) " and the variant of this term such as " comprising (comprising) ", " containing (comprises) " and " being included (comprised) ", be not intended to get rid of other additive, component, integer or step.
It being understood that invention that is open in this manual and that limit extends to the whole selective combination of two or more single features that are described or that can be found out by text or accompanying drawing.All these different combinations constitute each selectable aspect of the present invention.
Table 1: ilmenite is tested
Table 2: at 1000,1050,1100 and 1150 DEG C and 5.3%O2Oxygen concentration under heating YoganupRI in formed sintering mark
Table 3: by by the ilmenite in platinum ware at the O of 2.46 volume %2Middle oxidation 1 minute and the sintering that produces
Table 4: charcoal-CO2Gasification activity
Table 5: elementary analysis (% is in terms of dry coal)
The metallization speed of table 6:YoganupExtended, Wagerup, Cloverdale and Waroona sulfate ilmenite
Table 7: by the desired stove feed rate (at 1025 DEG C) of YoganupExtended, Wagerup, Cloverdale and Waroona sulfate ilmenite of reactive coal reduction
Table 8: by the SR grade produced after reactive coal reduction YoganupExtended, Wagerup, Cloverdale and Waroona sulfate ilmenite
Claims (21)
1. the method reclaimed as titania by titanium from the ilmenite of be unsuitable for standard Becher method, FeO > 12%, said method comprising the steps of:
In the presence of carbonaceous reducing agent, processing ilmenite in reducing atmosphere, thus ilmenite is converted into the ilmenite after reduction, wherein the iron oxides in ilmenite has been reduced into metallic iron, and described metallic iron separated thus obtain titania product
It is characterized in that, the described process to ilmenite is at high temperature carried out, and described high temperature is less than 1050 DEG C and is less than the TiO of titania product2Content is the highest but there is no the temperature reoxidized of metallic iron,
And it is further characterized in that, described carbonaceous reducing agent comprises the coal selected due to gasification activity, described gasification activity makes the rate of reduction of iron oxides and titanium material improve, and the most at least partly compensate for the relatively low TiO of the titania product caused by the described high temperature less than 1050 DEG C2Content, and have effectively achieved 90% or higher TiO in described titania product2Content.
Method the most according to claim 1, wherein, described gasification activity is sufficiently high to realize described compensation.
Method the most according to claim 2, wherein, the described gasification activity of coal is apparently higher than the meansigma methods of all coals.
The most according to the method in any one of claims 1 to 3, wherein, selected coal has the inorganic elements of one or more ions exchange of the sufficiently high impurity level to improve coal gasification speed, thus improves the reducing condition in described method and therefore improve the described rate of reduction of iron oxides and titanium material.
Method the most according to claim 4, wherein, the acid of the inorganic elements of one or more ions described exchange extraction unit can be divided at least 50%.
The most according to the method in any one of claims 1 to 3, wherein, selected coal is ub-bituminous coal or brown coal.
Method the most according to claim 6, wherein, the total moisture content of selected coal is 5 to 40%, the content of volatile material is more than 30% and content of ashes is less than 10%.
Method the most according to claim 6, wherein, the inherent moisture content of selected coal is 20% or less, and the content of volatile material is>40% and the content of ash be<5%.
The most according to the method in any one of claims 1 to 3, it is additionally included in before being transported to described process step, charcoal is mixed with ilmenite.
The most according to the method in any one of claims 1 to 3, wherein, the sulfur content of described coal is less than 1%w/w.
11. methods according to claim 10, wherein, the sulfur content of described coal is less than 0.5%.
12. methods according to claim 10, wherein, the sulfur content of described coal is less than 0.2%.
13. methods according to claim 10, are delivered to ilmenite mangana matter to be removed with the form of Manganese monosulfide. by sulfur during being additionally included in described process step, such conveying only later stage during reduction treatment is carried out.
14. according to the method in any one of claims 1 to 3, and wherein, the iron content represented with FeO in described ilmenite is less than 30%.
15. according to the method in any one of claims 1 to 3, and wherein, the free oxygen processed in atmosphere is not more than 2.5%.
16. according to the method in any one of claims 1 to 3, wherein, and the TiO reached in described titania product2Content is at least 93%.
17. according to the method in any one of claims 1 to 3, wherein, described in be unsuitable for the ilmenite of standard Becher method be the one in Primary ilmenite and hydridization ilmenite.
18. according to the method in any one of claims 1 to 3, wherein, described in be unsuitable for the ilmenite of standard Becher method be Ti content be 54-56%, Mg content be 1.5-2.5% and Cr content be the MurrayBasin ilmenite of 1%.
19. methods according to claim 4, wherein, the TiO reached in described titania product2Content is at least 93%.
20. methods according to claim 4, wherein, the sulfur content of described coal is less than 1%w/w.
21. methods according to claim 19, wherein, the sulfur content of described coal is less than 1%w/w.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2010901439 | 2010-04-06 | ||
| AU2010901439A AU2010901439A0 (en) | 2010-04-06 | Improved synthetic rutile process A | |
| PCT/AU2011/000390 WO2011123888A1 (en) | 2010-04-06 | 2011-04-06 | Improved synthetic rutile process a |
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| CN103201221A CN103201221A (en) | 2013-07-10 |
| CN103201221B true CN103201221B (en) | 2016-08-03 |
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| US (1) | US20130022522A1 (en) |
| EP (1) | EP2556026A1 (en) |
| CN (1) | CN103201221B (en) |
| AU (1) | AU2011238419B2 (en) |
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| IN2014CN00467A (en) * | 2011-07-28 | 2015-04-03 | Nokia Corp | |
| CN104561606A (en) * | 2014-11-21 | 2015-04-29 | 中国科学院过程工程研究所 | Clean technological method for preparing high-grade rich-titanium material by ilmenite |
| US10405299B2 (en) * | 2016-09-14 | 2019-09-03 | Qualcomm Incorporated | Reference signal transmission based on received signal quality |
| CN106521139A (en) * | 2017-01-05 | 2017-03-22 | 重庆大学 | Method for preparing high titanium slag through low temperature reduction and separation of titanium-containing iron ore |
| CN110372032A (en) * | 2019-08-19 | 2019-10-25 | 中国恩菲工程技术有限公司 | The method that titanium dioxide is prepared by ilmenite |
| CN113832280A (en) * | 2021-09-01 | 2021-12-24 | 新奥科技发展有限公司 | Method and apparatus for producing reduced ilmenite |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1923703A (en) * | 2005-09-01 | 2007-03-07 | 中南大学 | Method of preparing synthetic rutile from ore type ilmenite concentrate |
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| US4085190A (en) * | 1975-04-29 | 1978-04-18 | Chyn Duog Shiah | Production of rutile from ilmenite |
| ZA783519B (en) * | 1977-07-08 | 1979-10-31 | Ici Australia Ltd | A process for the beneficiation of titaniferous material |
| US5427749A (en) * | 1990-03-02 | 1995-06-27 | Wimmera Industrial Minerals Pty. Ltd. | Production of synthetic rutile |
| AU639178B2 (en) * | 1991-04-19 | 1993-07-15 | Rgc Mineral Sands Limited | Conversion of ilmenite to synthetic rutile e.g. by the becher process |
| GB0608080D0 (en) * | 2006-04-25 | 2006-05-31 | Warner Noel A | Co-production of steel, titanium and high-grade oxide |
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| CN1923703A (en) * | 2005-09-01 | 2007-03-07 | 中南大学 | Method of preparing synthetic rutile from ore type ilmenite concentrate |
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| Title |
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| 张家驹.攀矿直接还原用煤的选择.《冶金能源》.1992,第11卷(第5期),9-12. * |
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| Publication number | Publication date |
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| CN103201221A (en) | 2013-07-10 |
| US20130022522A1 (en) | 2013-01-24 |
| AU2011238419A1 (en) | 2012-11-01 |
| WO2011123888A1 (en) | 2011-10-13 |
| AU2011238419B2 (en) | 2013-03-28 |
| EP2556026A1 (en) | 2013-02-13 |
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