CN109402415A - A kind of preparation of low grade natural rutile can chlorination rich-titanium material method - Google Patents
A kind of preparation of low grade natural rutile can chlorination rich-titanium material method Download PDFInfo
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- CN109402415A CN109402415A CN201810786079.3A CN201810786079A CN109402415A CN 109402415 A CN109402415 A CN 109402415A CN 201810786079 A CN201810786079 A CN 201810786079A CN 109402415 A CN109402415 A CN 109402415A
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- natural rutile
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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
- C22B34/1213—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 wet processes, e.g. using leaching methods or flotation techniques
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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
- 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
- C22B34/1236—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 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching
- C22B34/124—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 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using acidic solutions or liquors
- C22B34/1245—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 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using acidic solutions or liquors containing a halogen ion as active agent
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a kind of low grade natural rutile preparation can chlorination rich-titanium material method, it is related to titanium chemical field, this method comprises the following steps: low grade natural rutile is carried out magnetic separation, obtain natural rutile concentrate and ilmenite, then to natural rutile concentrate be first added acid solution, add can ionize out in the solution fluorine ion leaching agent carry out Leach reaction, by being separated by solid-liquid separation, obtain solid material and acidleach mother liquor, solid material is washed until being in neutrality again, after through drying, can be prepared by it is qualified can chlorination rich-titanium material.The method energy consumption that the present invention uses is small, at low cost, process flow is short and environmentally friendly, not only has good impurity-eliminating effect, can greatly improve the TiO in natural rutile2Content, and the rate of recovery of titanium is high, can reach 95% or more.
Description
Technical field
The present invention relates to titanium chemical technology field, especially a kind of low grade natural rutile preparation can chlorination rich-titanium material
Method.
Background technique
At present after the natural rutile that beach placer selects part high-quality, there is also a large amount of TiO2The low product of < 85%
Position natural rutile, only E.I.Du Pont Company possesses directly using the such low grade natural rutile production chloride process titanium dioxide in part now
The chlorination technique of powder, but because its grade is low, impurity content is high, so the waste residue generated is more, chlorination furnace production efficiency is influenced, simultaneously
Also increase environmentally friendly difficulty；Low grade natural rutile can also be used in wlding industry, but its dosage is smaller.Therefore, most of low product
Position natural rutile cannot be utilized effectively since its grade is low, impurity content is high, cause originally rare natural golden red
The waste of stone resource.
Have the way directly smelted low grade natural rutile into acid-dissolved titanium slag in reality, but due to iron content is low,
Non-ferrous impurities content is high, so titanium grade is still lower after smelting, is only used for sulfuric acid process production titanium dioxide；To make
For the raw material for producing titanium white chloride powder, then also need to be modified it, then acidleach or alkali leaching decontamination, but the method work
Skill long flow path, processing cost is high, causes serious pollution to the environment.
Patent publication No. discloses " a kind of by microwave irradiation-magnetic separation-flotation connection for the Chinese patent of CN102357404A
Close technique improve grade of rutile method ", this method be the rutile ore after drying is put into microwave equipment irradiate after it is fast
Fast water cooling, then carry out ore grinding processing, will be levigate after rutile ore carry out magnetic separation separation, obtain iron ore concentrate and enrichment after gold
Hongshiite；Regulator is added in rutile ore after enrichment, adds inhibitor and collecting agent carries out flotation.Pass through this method
Obtained rich-titanium material chemical component can satisfy the ingredient requirement of production Titanium Dioxide Produced by Chloride Procedure, however the disadvantage is that first carry out micro-
Wave processing, but the application of enlargement is industrially not yet received in microwave equipment at present, to constrain industrial production；Followed by need
Ore grinding processing is carried out, this will lead to, and material is too thin, and elutriation amount increases, and titanium loss is big；Then, flotation has used inhibitor and has caught
Agent is received, wastewater treatment can be allowed difficult；It is finally that the tailing that floatingly selects in this method is more, about 30~40% TiO2It cannot function as chlorine
The raw materials for production of change method titanium dioxide use, so that the rate of recovery of titanium is lower.
The Chinese patent that patent publication No. is CN104045111B discloses " a method of prepare synthetic rutile ", this
Method carries out oxidation and modified with reduction using ilmenite concentrate and/or titanium slag as raw material, then with the sour Fluidizing Leaching of heating, filters,
It will be calcined after the washing of obtained solid material, obtain into synthetic rutile.The rich-titanium material chemical component that this method obtains can be with
Meet the requirement of Titanium Dioxide Produced by Chloride Procedure, the disadvantage is that process flow is complicated, energy consumption is high, it is at high cost, it is not applicable to natural rutile, it gives up
Acid processing is difficult, equipment seriously corroded, and synthetic rutile pulverization rate obtained is big, unfavorable to subsequent production titanium dioxide.
In view of by after the processing of low grade natural rutile, grade and impurity content can reach a kind of technique not yet both at home and abroad
To can chlorination rich-titanium material requirement, and make cost minimum simultaneously.Therefore, low grade natural rutile TiO is improved2Grade reduces
SiO2、ZrO2, the impurity contents such as FeO and calcium and magnesium, and its granularity is made to meet the production requirement of Titanium Dioxide Produced by Chloride Procedure, realizes serialization
Industrial production realizes low grade natural rutile resource utilization, becomes this field technical problem in the urgent need to address at present.
Summary of the invention
The purpose of the present invention is to provide a kind of low grade natural rutile preparation can chlorination rich-titanium material method, can
Consume that small, at low cost, process flow is simple, and finally obtain that high titanium grade, low impurity content and granularity be suitable for can chlorination richness titanium
Material.
The technical scheme adopted by the invention is that:
A kind of preparation of low grade natural rutile can chlorination rich-titanium material method, include the following steps: low grade natural
Rutile carries out magnetic separation, obtains natural rutile concentrate and ilmenite, and acid solution is first then added to natural rutile concentrate, adds again
The leaching agent for entering to ionize out fluorine ion in the solution carries out Leach reaction, by being separated by solid-liquid separation, obtains solid material and acidleach
Mother liquor, then solid material is washed until being in neutrality, after through drying, can be obtained can chlorination rich-titanium material.
The present invention is natural what is obtained after magnetic separation for remaining low grade natural rutile after beach placer screening
First be added in rutile concentrate acid solution carry out leaching process, after again using leaching agent improve acidleach effect, thus realize removal of impurities,
Promote the purpose of natural rutile titanium grade.The present invention carries out first time screening and removing impurities to low grade natural rutile first, i.e.,
By magnetic separation, the ilmenite in natural rutile is removed, wherein since beach placer granularity itself is smaller, so no longer needing to low
Grade natural rutile carries out ore grinding processing, and directly carries out magnetic separation；And acid solution and leaching agent is added to natural golden
Red stone concentrate carries out Leach reaction, implements programmed screening removal of impurities；SiO is mainly contained in natural rutile concentrate2、ZrO2、FeO、
The impurity such as calcium and magnesium, acid solution, which is first added, to dissolve away the impurity such as FeO, calcium and magnesium from natural rutile concentrate, make iron calcium and magnesium etc.
Ion enters in solution, realizes the separation of the impurity such as iron calcium and magnesium and natural rutile；But SiO therein2、ZrO2Impurity by
It is more stable in chemical property, it does not react with water under general case, is not also reacted with general acid, so the acid solution of front cannot
By SiO2、ZrO2It dissolves away, therefore just needs to add leaching agent, leaching agent is fluoride, provides fluorine ion, and leaching agent is added just
Energy acid dissolves away SiO2、ZrO2, this is because SiO2、ZrO2Although cannot be reacted with general acid, hydrofluoric acid can be dissolved in and heat is dense
Phosphoric acid, in the solution hydrofluoric acid and SiO2Reaction can generate fluosilicic acid soluble easily in water, as long as so guaranteeing natural rutile
There is hydrofluoric acid, so that it may by SiO in acid dip solution2It dissolves away, so that it be removed from natural rutile concentrate.
As for why not leaching to natural rutile concentrate most starting to be directly added into a kind of substance of hydrofluoric acid, this
It is to show that leaching low grade natural rutile impurity-eliminating effect using single hydrofluoric acid does not use nitration mixture effect good because testing,
During entire acidleach, only a small amount of fluorine ion, which need to be added, can reach better effects as reaction promoter；In addition, only using hydrogen
Fluoric acid dosage is big, at high cost, severe corrosion to equipment.
And the TiO in natural rutile2, property is extremely stable, hardly reacts with other substances under room temperature, only
The concentrated sulfuric acid and hydrofluoric acid can be just completely dissolved under the conditions of boiling for a long time by having, and for TiO2For hydrofluoric acid, even
It is under conditions of boiling, their reaction is all the very slowly TiO of only a small part2By hydrofluoric acid dissolution,
Even if but in the present invention Leach reaction when extraction temperature be 100 DEG C, extraction time 48h, the rate of recovery of titanium can also reach
95% or more.Therefore, the impurity in low grade natural rutile can be effectively removed by above-mentioned processing method, mentioned significantly
The titanium grade of high natural rutile, and it is solid material isolated after acidleach is washed, dry, so that it may it is moderate to obtain granularity
Qualification can chlorination rich-titanium material, while entire process flow is simple, of short duration, and energy consumption is also small, and processing cost is also relatively low, in the process
The loss of titanium is few, so that the rate of recovery of titanium is high.
The acid solution is the combination of one or more of hydrochloric acid, sulfuric acid, phosphoric acid.
The mass concentration of the acid solution is 2~50%, and the liquid-solid ratio of the acid solution and natural rutile concentrate is 1.5~5:
1.Using pickle and reasonable acid solution dosage, the effect of dissolved impurity can not only be fully achieved, and saved resource with
Cost, while reducing the processing difficulty of waste liquid below.
The leaching agent is one or more of hydrofluoric acid, ammonium fluoride, sodium fluoride, potassium fluoride, ammonium acid fluoride group
It closes.Leaching agent is fluoride, provides fluorine ion, hydrofluoric acid is formed with the hydrogen ion in acid solution, thus by SiO2、ZrO2It dissolves away, reaches
To the purpose for removing impurity in natural rutile.
The dosage of the leaching agent is the 1~50% of natural rutile concentrate quality used.According to be processed low-grade
SiO in natural rutile2The content of impurity carrys out reasonable employment leaching agent, can effectively remove SiO2, and can be reduced cost, drop
The low fluorine removal workload that solution is carried out below.
The temperature when leaching is 0~100 DEG C, and extraction time is 1~48h, and leaching pressure is normal pressure.With acid solution to day
When right rutile carries out Leach reaction, suitable temperature can promote the effect of the molten impurity of acid, and according to miscellaneous in natural rutile
The composition of matter could make Leach reaction complete by certain reasonable time, guarantee being dissolved for impurity maximum possible, thus
Improve the titanium grade of finally obtained natural rutile；In addition, the present invention only needs smooth, the good completion leaching of energy under normal pressure
It reacts out, does not need to pressurize, it is low for equipment requirements.
Further, solid material obtained after the separation of solid and liquid is washed at normal temperature with deionized water, every time
Deionized water and the liquid-solid ratio of solid material are 2~5:1 when washing, are washed until solid material cleaning solution is in neutrality, so
It is dried at 105~120 DEG C afterwards to get to can chlorination rich-titanium material.It is inevitably deposited in the solid material obtained after separation of solid and liquid
In a little foreign ion, and in acidity, so needing to use solid material in order to not influence solid material in application later
Deionized water is washed, until being in neutrality, while washing also to take science means, according to certain liquid-solid ratio into
Row repeatedly washing, not only saves deionized water, but also realize the purpose of washing in this way.
Calcium salt is first added in the acidleach mother liquor, then adds aluminium salt, magnesium salts and/or phosphate and is handled, through filtering,
Obtain waste water and waste residue.
If simple by adding the chemicals such as calcium salt into acidleach mother liquor waste water, react calcium ion with fluorine ion
Generate CaF2Precipitating, to realize that removing makes the F in waste water-Purpose, the simple process is convenient, and expense is low, but there are it is some not
Foot, i.e., after fluorine in wastewater content that treated reaches 15mg/L, then plus calcium salt, be hardly formed sediment, therefore this method is generally suitable
Coagulation or pretreatment together in high-concentration fluorine-containing waste water, are extremely difficult to national standard primary standard, the CaF in addition generated2It is heavy
Shallow lake can be wrapped in Ca (OH)2The surface of particle, therefore calcium salt cannot be fully utilized, and cause to waste.
If, in addition aluminium salt, magnesium salts, phosphate etc., not only defluorination effect increases, but also simultaneously but on the basis of adding calcium salt
Improve the utilization rate of calcium salt.For example, magnesium salts is added on the basis of adding lime, made by lime and the aqueous solution containing magnesium salts
With generation magnesium hydrate precipitate realizes the absorption to fluoride；The aluminium salts such as aluminum sulfate, alum are added in waste water, hydrogen can be generated
Aluminium oxide, aluminium hydroxide and fluorine ion, which react, in coagulation process produces fluorine aluminium complex, the fluorine aluminium complex quilt of production
Aluminium hydroxide alumen ustum adsorbs and generates precipitating, to achieve the purpose that fluorine removal；Suction of these precipitate metal hydroxides to fluorine ion
Attached coprecipitated effect, if can make fluoro-containing concentration that can be down to 8mg/L hereinafter, and plus lime to pH value of solution=11~12, then plus sulfuric acid
Aluminium, makes pH=6~8, then forming aluminium hydroxide can make fluoro-containing concentration be down to 5mg/L or less；If plus while lime, phosphorus is added
Hydrochlorate (such as calcium superphosphate, disodium hydrogen phosphate), the then apatite that indissoluble can be formed with fluorine in water precipitate.Further, it is also possible in water
Middle addition high polymer polyacrylamide makees flocculant, mainly for obtaining better sedimentation effect, can not increase existing place
On the basis of managing equipment, better fluorine removal improves the treatment effect of waste water.Acidleach mother liquor is handled by the method, it can
So that obtained waste water reaches " industrial wastewater discharge standard ", the purpose of clean manufacturing is fully achieved.
The calcium salt is the combination of one or more of calcium oxide, calcium hydroxide, calcium chloride, calcium carbide.Calcium is provided
Ion, mainly for generating CaF with fluorine ion2, thus the Removal of F- ion from solution.
The waste water is used as the water distribution of configuration acid solution, and the waste residue is for producing cement.The waste water of generation, waste residue are recycled
It utilizes, turns waste into wealth, sufficiently, resource is effectively utilized, is very beneficial for environmental protection.
Preferably, the acidleach Recycling Mother Solution is for leaching natural rutile concentrate.Wherein also contain a small amount of hydrogen
Ion can participate in the Leach reaction of natural rutile.
TiO in the low grade natural rutile2Content is 60~85%.
The ilmenite is for smelting acid-dissolved titanium slag.
The beneficial effects of the present invention are: method energy consumption of the invention is small, at low cost, process flow is simple and friendly to environment
It is good；And after good impurity removing effect, especially low grade natural rutile take targeting to remove silicon, removal rate >=70% of silicon, than making
Good, low in cost, the TiO in natural rutile after processing with alkali leaching effect2Content can reach 85% or more, and granularity is moderate, completely
Requirement of the Titanium Dioxide Produced by Chloride Procedure to raw material can be reached；Secondly the rate of recovery of titanium is high, can reach 95% or more；The present invention simultaneously
Compared with the prior art, TiO2Promotion amplitude is larger, can reach 50%, therefore, can handle TiO2The lower natural golden of grade
Red stone, reach can chlorination rich-titanium material requirement.
Detailed description of the invention
Fig. 1 is process flow diagram of the invention.
Specific embodiment
Present invention will be further explained below with reference to the attached drawings and examples.
Embodiment 1
By low grade natural rutile (part of constituent content are as follows: TiO2: 60.17%, SiO2: 3.16%, CaO:
0.31%, MgO:0.57%) high intensity magnetic separation is carried out, isolate natural rutile concentrate and ilmenite；Weigh 100g natural rutile
Concentrate, first be added concentration be 18% HCl solution, liquid-solid ratio press 4:1, after add concentration be 40% HF solution and NH4F is solid
Body is leached as leaching agent, and the dosage of HF solution is 1.0%, NH of natural rutile concentrate quality used4The dosage of F solid
It is the 2.5% of natural rutile concentrate quality used, Leach reaction temperature is 80 DEG C, and the Leach reaction time is 2h, leaches pressure
For normal pressure, then it is separated by solid-liquid separation；The solid material separated is washed with deionized water, liquid-solid ratio presses 3:1, washes
After washing 3 times, filtering, then by the material of filtering at 110 DEG C dry 3 hours to get to can chlorination rich-titanium material；It is isolating again
It is the quick lime of 0.20g/L and the calcium chloride of 0.08g/L that concentration after being dissolved in acidleach mother liquor is added in the acidleach mother liquor come, to remove
The MgSO that concentration is 0.05g/L after being dissolved in acidleach mother liquor is added in the impurity such as the fluorine ion in solution afterwards4Solution removes extra F-,
It adds sodium carbonate and removes calcium and magnesium ion, filtering obtains qualified waste water, can return to the water distribution as configuration acid solution.
Through detecting, gained can constituent part content in chlorination rich-titanium material are as follows: TiO2: 89.07%, CaO:0.12%, MgO:
0.18%, SiO2: 0.93%；The rate of recovery of titanium is 96.34%, and 60~140 mesh granularities account for 84.07%, meet chloride process titanium dioxide
Powder raw material requirement.
Embodiment 2
By low grade natural rutile (part of constituent content are as follows: TiO2: 75.96%, SiO2: 3.74%, CaO:
0.24%, MgO:0.37%) high intensity magnetic separation is carried out, isolate natural rutile concentrate and ilmenite；Weigh 100g natural rutile
The H that concentration is 20% is first added in concentrate2SO4Solution, liquid-solid ratio press 3:1, after add concentration be 40% HF solution help leaching
Agent is leached, and the dosage of HF solution is the 4.0% of natural rutile concentrate quality used, and Leach reaction temperature is 80 DEG C, leaching
The reaction time is 1h out, and leaching pressure is normal pressure, is then separated by solid-liquid separation；To the solid material deionized water separated
It is washed, liquid-solid ratio presses 3:1, and after washing 3 times, then the material of filtering is dried 3 hours at 110 DEG C to get arriving by filtering
It can chlorination rich-titanium material；The quick lime that concentration is 0.25g/L after being dissolved in acidleach mother liquor is added in the acidleach mother liquor separated again
With the calcium carbide of 0.1g/L, filtered after reaction, filtrate adds be dissolved in filtrate after concentration be 0.05g/L Al2(SO4)3Solution and
The Na of 0.10g/L3PO4Solution removes extra F-, and make flocculant with polyacrylamide, it filters, obtains qualified waste water.
Through detecting, gained can constituent part content in chlorination rich-titanium material are as follows: TiO2: 92.73%, CaO:0.05%, MgO:
0.09%, SiO2: 1.14%；The rate of recovery of titanium is 97.11%, and 60~140 mesh granularities account for 86.17%, meet chloride process titanium dioxide
Powder raw material requirement.
Embodiment 3
By low grade natural rutile (part of constituent content are as follows: TiO2: 68.74%, SiO2: 4.20%, CaO:
0.41%, MgO:0.34%) high intensity magnetic separation is carried out, isolate natural rutile concentrate and ilmenite；Weigh 100g natural rutile
The H that concentration is 15% is first added in concentrate2SO4Solution and 20% phosphoric acid solution, liquid-solid ratio press 3:1, after add NaF solid and
KF solid is leached as leaching agent, and the dosage of NaF solid is 2.0%, the KF solid of natural rutile concentrate quality used
Dosage is the 23% of natural rutile concentrate quality used, and Leach reaction temperature is 94 DEG C, and the Leach reaction time is 1h, leaches pressure
Power is normal pressure, is then separated by solid-liquid separation；The solid material separated to be washed with deionized water, liquid-solid ratio presses 3:1,
After washing 3 times, filtering, then by the material of filtering at 110 DEG C dry 3 hours to get to can chlorination rich-titanium material；It is separating again
The CaCl that concentration is 0.34g/L after being dissolved in acidleach mother liquor is added in acidleach mother liquor out2, filtered after reaction, then in filtrate
The Al that concentration after being dissolved in filtrate is 0.12g/L is added2(SO4)3Solution removes extra F-, make flocculant, mistake with polyacrylamide
Filter obtains qualified waste water, returns to the water distribution as configuration acid solution.
Through detecting, gained can constituent part content in chlorination rich-titanium material are as follows: TiO2: 88.61%, CaO:0.13%, MgO:
0.18%, SiO2: 1.12%；The rate of recovery of titanium is 97.39%, and 60~140 mesh granularities account for 85.36%, meet chloride process titanium dioxide
Powder raw material requirement.
Embodiment 4
By low grade natural rutile (part of constituent content are as follows: TiO2: 72.42%, SiO2: 2.17%, CaO:
0.17%, MgO:0.24%) high intensity magnetic separation is carried out, isolate natural rutile concentrate and ilmenite；Weigh 100g natural rutile
The H that concentration is 30% is first added in concentrate2SO4Solution, liquid-solid ratio press 5:1, after add concentration be 40% HF solution and
NH4HF2Solid is leached as leaching agent, and the dosage of HF solution is 6.0%, NH of natural rutile concentrate quality used4HF2
The dosage of solid is the 1.0% of natural rutile concentrate quality used, and Leach reaction temperature is room temperature, and the Leach reaction time is
For 24 hours, leaching pressure is normal pressure, is then separated by solid-liquid separation；The solid material separated is washed with deionized water, liquid
Gu after washing 3 times, filtering, then that the material of filtering is 3 hours dry at 110 DEG C, obtaining can chlorination rich-titanium material than pressing 3:1；
The calcium hydroxide and 0.20g/L that concentration after being dissolved in acidleach mother liquor is 0.10g/L is added in the acidleach mother liquor separated again
Quick lime filters after reaction, then is added in filtrate and is dissolved in the MgSO that concentration after filtrate is 0.05g/L4Solution and 0.05g/L's
Na3PO4Solution removes extra F-, make flocculant with polyacrylamide, filter, obtain qualified waste water.
Through detecting, gained can constituent part content in chlorination rich-titanium material are as follows: TiO2: 88.28%, CaO:0.09%, MgO:
0.12%, SiO2: 0.53%；The rate of recovery of titanium is 96.48%, and 60~140 mesh granularities account for 83.16%, meet chloride process titanium dioxide
Powder raw material requirement.
Claims (13)
1. a kind of preparation of low grade natural rutile can chlorination rich-titanium material method, it is characterized in that: including the following steps: low product
Position natural rutile carries out magnetic separation, obtains natural rutile concentrate and ilmenite, acid is first then added to natural rutile concentrate
Liquid, add can ionize out in the solution fluorine ion leaching agent carry out Leach reaction, through separation of solid and liquid, obtain solid material
With acidleach mother liquor, then solid material is washed until being in neutrality, after through drying, can be prepared by can chlorination richness titanium
Material.
2. a kind of low grade natural rutile preparation as described in claim 1 can chlorination rich-titanium material method, it is characterized in that: institute
Acid solution is stated as the combination of one or more of hydrochloric acid, sulfuric acid, phosphoric acid.
3. a kind of low grade natural rutile preparation as described in claim 1 can chlorination rich-titanium material method, it is characterized in that: institute
The mass concentration for stating acid solution is 2~50%, and the liquid-solid ratio of the acid solution and natural rutile concentrate is 1.5~5:1.
4. a kind of low grade natural rutile preparation as described in claim 1 can chlorination rich-titanium material method, it is characterized in that: institute
Leaching agent is stated as the combination of one or more of hydrofluoric acid, ammonium fluoride, sodium fluoride, potassium fluoride, ammonium acid fluoride.
5. a kind of low grade natural rutile preparation as described in claim 1 can chlorination rich-titanium material method, it is characterized in that: institute
The dosage for stating leaching agent is the 1~50% of natural rutile concentrate quality used.
6. a kind of low grade natural rutile preparation as described in claim 1 can chlorination rich-titanium material method, it is characterized in that: institute
Stating temperature when leaching is 0~100 DEG C, and extraction time is 1~48h, and leaching pressure is normal pressure.
7. a kind of low grade natural rutile preparation as described in claim 1 can chlorination rich-titanium material method, it is characterized in that: institute
It states the solid material obtained after being separated by solid-liquid separation to be washed at normal temperature with deionized water, every time deionized water and solid when washing
The liquid-solid ratio of material is 2~5:1, washs until solid material cleaning solution is in neutrality, then carries out at 105~120 DEG C
It is dry to get to can chlorination rich-titanium material.
8. a kind of low grade natural rutile preparation as described in claim 1 can chlorination rich-titanium material method, it is characterized in that: institute
It states acidleach mother liquor and calcium salt is first added, then add aluminium salt, magnesium salts and/or phosphate and handled, filtered, obtain waste water and give up
Slag.
9. a kind of low grade natural rutile preparation as claimed in claim 8 can chlorination rich-titanium material method, it is characterized in that: institute
Calcium salt is stated as the combination of one or more of calcium oxide, calcium hydroxide, calcium chloride, calcium carbide.
10. a kind of low grade natural rutile preparation as claimed in claim 8 can chlorination rich-titanium material method, it is characterized in that:
The waste water is used as the water distribution of configuration acid solution, and the waste residue is for producing cement.
11. a kind of low grade natural rutile preparation as described in claim 1 can chlorination rich-titanium material method, it is characterized in that:
The acidleach Recycling Mother Solution is for leaching natural rutile concentrate.
12. a kind of low grade natural rutile preparation as described in claim 1 can chlorination rich-titanium material method, it is characterized in that:
TiO in the low grade natural rutile2Content is 60~85%.
13. a kind of low grade natural rutile preparation as described in claim 1 can chlorination rich-titanium material method, it is characterized in that:
The ilmenite is for smelting acid-dissolved titanium slag.
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| CN112520786B (en) * | 2020-12-01 | 2022-08-23 | 成都工业学院 | Acid-soluble titanium-rich material and preparation method and application thereof |
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| CN114807591B (en) * | 2022-03-16 | 2023-12-15 | 中南大学 | Method for preparing high-quality titanium-rich material by deep impurity removal of ilmenite |
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