CN110482601A - It is a kind of to produce TiO with rutile ore2The method of powder - Google Patents
It is a kind of to produce TiO with rutile ore2The method of powder Download PDFInfo
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- CN110482601A CN110482601A CN201910860296.7A CN201910860296A CN110482601A CN 110482601 A CN110482601 A CN 110482601A CN 201910860296 A CN201910860296 A CN 201910860296A CN 110482601 A CN110482601 A CN 110482601A
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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
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract
TiO is produced with rutile ore the invention discloses a kind of2The method of powder belongs to technical field of mineral processing, of the present invention to produce TiO with rutile ore2The method of powder leaches rutile ore using fluoride process, and titanium elements are reacted with fluorine ion enters solution in the form of fluorine-containing complex ion, and other impurities element and fluorine ion form fluoride precipitating, realizes the purpose of Selectively leaching titanium elements.It is of the present invention to produce TiO with rutile ore2The method of powder, impurity element finally exist with oxide or harmless fluoride form, can be used as making steel flux, realize the purpose without waste sludge discharge.The present invention, as impurity removal reagents and hydrolysing agent, does not introduce excessive moisture using liquefied ammonia while being adjustable pH value and ammonium ion content, reduce amount of filtrate, it is ensured that fluorine-containing to recycle containing ammonium reagent.
Description
Technical field
The invention belongs to technical field of mineral processing, and in particular to a kind of to produce TiO with rutile ore2The method of powder.
Background technique
Titanium is important rare metal, titanium products mainly have Titanium, titanium alloy, titanium dioxide (titanium white), titanium tetrachloride,
Titanium carbonitride and barium metatitanate etc..Wherein, titanium dioxide is as main titanium products, have chemical property stabilization, strong covering power,
The features such as color power is strong, heat-resist, resistance to acid and alkali is strong, good dispersion, be widely used in building coating, other coating, plastics,
The industries such as papermaking, ink, fiber have consequence and effect in the national economic development.The titanium material quilt in the whole world 90%
For producing titanium dioxide, China's titanium dioxide annual output is in rise year by year trend more than 2,800,000 tons.
The titaniferous materials of Ti industry mainly have ilmenite, rutile ore, perovskite etc., although China's Panxi Diqu preservation has
A large amount of v-ti magnetite ore resources, but because of its calcium-magnesium content height, it is low to lead to climb western titanium resource utilization rate, China's titanium resource import according to
Bad degree is for a long time 40% or more.China's rutile ore is mainly distributed on the ground such as Hubei, Henan, Shaanxi, Jiangsu, Shanxi and Shandong,
But good rutile ore resource is few, China rutile ore raw ore TiO2Grade is low, fine size, miscellaneous in dressing product rutile ore
Matter content is more, big using difficulty.Therefore, a kind of TiO is produced with rutile ore from developing2The method of powder, to alleviation China
There is lack of raw materials that status is of great significance for Ti industry.
Currently, the production method of titanium dioxide is mainly sulfuric acid process and two kinds of fluidizing chlorination method, it is big, useless to there is acid consumption in sulfuric acid process
Acid amount is big, the serious problem of environmental pollution.Fluidizing chlorination method needs TiO in raw material to ingredient requirement height2>90%, CaO<
0.2%, MgO < 1%, and chloridising can generate chloride residue, chloride residue harmless treatment is difficult.Rutile structure is stablized, it is difficult to
It is decomposed by the concentrated sulfuric acid, cannot function as the raw material of sulfate process titanium dioxide, impurity content is higher in China's rutile ore, especially calcium and magnesium
Impurity needs that fluidizing chlorination furnace charge could be used as by being further processed removal of impurities, causes rutile ore using long flow path, energy consumption
Height, and easily cause damages to environment.Therefore, develop it is a kind of can clean and effective with rutile ore produce TiO2The method of powder is right
China's titanium white industrial expansion and titanium resource are all of great significance using horizontal raising.
Summary of the invention
More for impurity content in rutile ore in the prior art, using the big problem of difficulty, the purpose of the present invention exists
In provide it is a kind of efficiently, low cost, clean produce TiO with rutile ore2The method of powder.
The present invention, which provides, a kind of produces TiO with rutile ore2The method of powder, comprising the following steps:
(1) rutile ore is added to fluorination leaching agent to leach, after separation of solid and liquid, obtains leached mud and titaniferous leaches
Liquid；
(2) pyrohydrolysis processing is carried out to through the resulting leached mud of step (1), it is made to be changed into harmless oxide, it is described
The ammonia and hydrogen fluoride return step (1) of generation are recycled in pyrohydrolysis process；
(3) removal of impurities processing is carried out to through the resulting titaniferous leachate of step (1), after separation of solid and liquid, obtain titanium liquid and impurity
Precipitating, return step (1) after contamination precipitation is dissolved by fluorination leaching agent；
(4) it is hydrolyzed to through the resulting titanium liquid of step (3), after separation of solid and liquid, obtains TiO2Presoma；
(5) to through step (4) resulting TiO2Presoma obtains TiO by pyrohydrolysis and calcining transformation2Powder, the heat
The ammonia and hydrogen fluoride return step (1) of generation are recycled in hydrolytic process.
Preferably, in step (1), the fluorination leaching agent is fluorine-containing containing ammonium circulation reagent, [F-] concentration be 5~
20mol/L, [NH4 +]/[F-] molar ratio be 0~1, pH value be -1~7, pH value react [H+] concentration, determine titaniferous materials
Leach reaction speed determines leaching efficiency；If fluorine-containing containing [F in ammonium circulation reagent-] concentration and when pH value not up to standard, it is returned with process
The HF of receipts is supplemented；[NH4 +] concentration deficiency when with process recycle NH3Supplement.
It is furthermore preferred that the pH value is -1~0.
Preferably, in step (1), the leaching process, solid-to-liquid ratio is 10~200g/L, and extraction temperature is 20~160
DEG C, extraction time is in 10~180min.
Preferably, in step (2), the pyrohydrolysis temperature is 200~600 DEG C, and the time is 30~180min.
Preferably, in step (3), the impurity removal reagents are liquefied ammonia, and the pH value that cleans is between 5.5~9.0, and clean temperature
Between 20~100 DEG C, except miscellaneous time is between 5~120min.
Preferably, in step (3), the course of dissolution, solution temperature be 20~100 DEG C, dissolution time be 5~
120min。
Preferably, in step (4), the hydrolysing agent is liquefied ammonia, hydrolyzes pH value between 7.5~14.0, hydrolysis temperature
Degree is between 20~100 DEG C, and hydrolysis time is between 5~120min.
Preferably, in step (5), the pyrohydrolysis temperature is 200~600 DEG C, and the time is 30~180min.
Preferably, in step (5), the calcining transformation temperature is 600~900 DEG C, and the time is 30~180min.
The principle of technical solution of the present invention are as follows:
The present invention proposes to extract TiO using fluoride process using rutile ore as raw material2The technical solution of powder, the technical side
Case passes through with containing [NH4 +] and [F-] leaching agent Selectively leaching rutile ore in titanium elements, be changed into it soluble
TiF6 2-Complex ion, other impurities are formed precipitating in the form of fluorine-containing ammonium salt or fluoride and stayed in leached mud.Containing in leached mud
Fluorine ammonium salt is changed into harmless oxide or fluoride after pyrohydrolysis, circulation after the fluorine and ammonia that pyrohydrolysis process generates are recovered
Make leaching agent.Resulting leachate adjusts pH of leaching solution and [NH through liquefied ammonia is added4 +] concentration, promotion residual impurity element (iron,
Manganese, vanadium, chromium) fluorine-containing ammonium salt precipitating is formed, return to fluorination leaching step.Titanium liquid after removal of impurities be added liquefied ammonia adjust pH value and
[NH4 +] concentration, make wherein titanium component precipitate to form TiO2Presoma.Resulting TiO2Presoma through pyrohydrolysis and calcining transformation at
For anatase titanium dioxide or rutile TiO2Powder, circulation makees leaching agent after the fluorine and ammonia that pyrohydrolysis process generates are recovered, thus real
The now high efficiency extraction TiO from rutile ore2, the invention mainly relates to chemical reaction it is as follows:
TiO2+6F-+4H+=TiF6 2-+2H2O (1)
CaO+2F-+2H+=CaF2↓+H2O (2)
MgO+2F-+2H+=MgF2↓+H2O (3)
Fe2O3+12F-+6NH4 ++6H+=2 (NH4)3FeF6↓+3H2O (4)
Al2O3+12F-+6NH4 ++6H+=2 (NH4)3AlF6↓+3H2O (5)
SiO2+6F-+4H+=SiF6 2-+2H2O (6)
TiF6 2-+2NH4 ++2OH-=(NH4)2TiOF4↓+2F-+H2O (7)
(NH4)2TiOF4+H2O=TiO2+2NH3↑+4HF↑ (8)
Advantageous effects of the invention:
(1) of the present invention to produce TiO with rutile ore2The method of powder leaches rutile ore, titanium member using fluoride process
Element is reacted with fluorine ion enters solution in the form of fluorine-containing complex ion, other impurities element, especially calcium and magnesium impurity and fluorine ion shape
It is precipitated at fluoride, realizes the purpose of Selectively leaching titanium elements.The present invention is low to rutile ore ingredient requirement, and it is miscellaneous not limit its
Prime element type and content, are compared with other methods, and have the advantages that wide to adaptability to raw material.
(2) of the present invention to produce TiO with rutile ore2The method of powder, impurity element is finally with oxide or harmless
Fluoride form exist, can be used as make steel flux, realize the purpose without waste sludge discharge.Fluorine-containing ammonium salt stability is poor, technique
The reagent of fluorine-containing and ammonium used in process can heated recovery be recycled, realize the mesh without exhaust gas, discharge of wastewater
's.Compared with current sulfuric acid process and chloridising, have the advantages that discharge without " three wastes ", it can be achieved that cleanly production.With chloridising
It compares, technical process reaction temperature is low, and operational safety is relatively high.
(3) present invention uses liquefied ammonia as impurity removal reagents and hydrolysing agent, while being adjustable pH value and ammonium ion content
Excessive moisture is not introduced, amount of filtrate is reduced, it is ensured that is fluorine-containing to be recycled containing ammonium reagent.
Detailed description of the invention
Fig. 1 is the process flow chart of the embodiment of the present invention 1.
Specific embodiment
Following embodiment is intended to further illustrate the content of present invention, rather than limits the scope of the invention.
In embodiments of the present invention, unless otherwise instructed, the means of use are the means of this field routine, the examination of use
Agent can be obtained by conventional commercial sources.
Embodiment 1
Certain rutile concentrate, contains 92.21%TiO2, granularity be -74 μm account for 86.4%, leaching agent [NH4 +]T/[F]TRatio
It is 0.3, [F]TConcentration is 12mol/L, and pH value is -0.65, is to be soaked after 120g/L is mixed with fluorination leaching agent by solid-to-liquid ratio
It tests out, extraction temperature is 140 DEG C, extraction time 60min.After leaching, leached mud and leachate is obtained by filtration, is leached
Slag passes through the pyrohydrolysis 1h at 450 DEG C and removes ammonia therein and fluorine, adjusts pH value to leachate addition liquefied ammonia and is removed to 7.0
Miscellaneous, removal of impurities temperature is 60 DEG C, time 45min, obtains precipitating and titanium liquid after filtering, precipitating returns to leaching process, to titanium liquid
It liquefied ammonia is added adjusts pH value and be hydrolyzed to 13, temperature is 60 DEG C, time 30min, obtains TiO through filtering2Presoma, it is right
TiO2Presoma carries out pyrohydrolysis and calcination processing, pyrohydrolysis system are as follows: temperature is 450 DEG C, time 1h, calcinating system are as follows:
Temperature is 850 DEG C, time 2h, obtains and contains 99.56%TiO2Anatase titanium dioxide TiO2Powder, concrete technology flow process are as shown in Figure 1.
Embodiment 2
Certain rutile concentrate, contains 90.42%TiO2, granularity be -74 μm account for 82.2%, leaching agent [NH4 +]T/[F]TRatio
It is 0.2, [F]TConcentration is 10mol/L, and pH value is -0.60, is to be soaked after 100g/L is mixed with fluorination leaching agent by solid-to-liquid ratio
It tests out, extraction temperature is 140 DEG C, extraction time 60min.After leaching, leached mud and leachate is obtained by filtration, is leached
Slag passes through the pyrohydrolysis 1h at 400 DEG C and removes ammonia therein and fluorine, adjusts pH value to leachate addition liquefied ammonia and is removed to 7.5
Miscellaneous, removal of impurities temperature is 60 DEG C, time 30min, obtains precipitating and titanium liquid after filtering, precipitating returns to leaching process, to titanium liquid
It liquefied ammonia is added adjusts pH value and be hydrolyzed to 12, temperature is 60 DEG C, time 25min, obtains TiO through filtering2Presoma, it is right
TiO2Presoma carries out pyrohydrolysis and calcination processing, pyrohydrolysis system are as follows: temperature is 400 DEG C, time 1h, calcinating system are as follows:
Temperature is 800 DEG C, time 2h, obtains and contains 99.42%TiO2Anatase titanium dioxide TiO2Powder.
Embodiment 3
Certain rutile concentrate, contains 87.05%TiO2, granularity be -45 μm account for 76.4%, leaching agent [NH4 +]T/[F]TRatio
It is 0.3, [F]TConcentration is 10mol/L, and pH value is -0.54, is to be soaked after 100g/L is mixed with fluorination leaching agent by solid-to-liquid ratio
It tests out, extraction temperature is 120 DEG C, extraction time 60min.After leaching, leached mud and leachate is obtained by filtration, is leached
Slag passes through the pyrohydrolysis 1h at 400 DEG C and removes ammonia therein and fluorine, adjusts pH value to leachate addition liquefied ammonia and is removed to 8.0
Miscellaneous, removal of impurities temperature is 60 DEG C, time 30min, obtains precipitating and titanium liquid after filtering, precipitating returns to leaching process, to titanium liquid
It liquefied ammonia is added adjusts pH value and be hydrolyzed to 12, temperature is 60 DEG C, time 30min, obtains TiO through filtering2Presoma, it is right
TiO2Presoma carries out pyrohydrolysis and calcination processing, pyrohydrolysis system are as follows: temperature is 400 DEG C, time 1h, calcinating system are as follows:
Temperature is 800 DEG C, time 2h, obtains and contains 99.51%TiO2Anatase titanium dioxide TiO2Powder.
Comparative example
Certain rutile concentrate, contains 90.42%TiO2, granularity be -74 μm account for 82.2%, in mass ratio with 98% concentrated sulfuric acid
1:2 is heated to 250 DEG C of acidleach after mixing, and 2h is cured at a temperature of 250 DEG C, and solid is through adding water to leach at 60 DEG C after curing
2h, titanium leaching rate is 3.61% in rutile concentrate.
The above is only a preferred embodiment of the present invention, protection scope of the present invention is not limited merely to above-mentioned implementation
Example.To those of ordinary skill in the art, obtained improvement and change in the case where not departing from the technology of the present invention concept thereof
It changes and also should be regarded as protection scope of the present invention.
Claims (9)
1. a kind of produce TiO with rutile ore2The method of powder, which comprises the following steps:
(1) rutile ore is added to fluorination leaching agent to leach, after separation of solid and liquid, obtains leached mud and titaniferous leachate；
(2) pyrohydrolysis processing is carried out to through the resulting leached mud of step (1), it is made to be changed into harmless oxide, the hot water
The ammonia and hydrogen fluoride return step (1) of generation are recycled in solution preocess；
(3) removal of impurities processing is carried out to through the resulting titaniferous leachate of step (1), after separation of solid and liquid, obtain titanium liquid and contamination precipitation,
Return step (1) after contamination precipitation is dissolved by fluorination leaching agent；
(4) it is hydrolyzed to through the resulting titanium liquid of step (3), after separation of solid and liquid, obtains TiO2Presoma；
(5) to through step (4) resulting TiO2Presoma obtains TiO by pyrohydrolysis and calcining transformation2Powder, the pyrohydrolysis
The ammonia and hydrogen fluoride return step (1) of generation are recycled in the process.
2. according to claim 1 produce TiO with rutile ore2The method of powder, which is characterized in that in step (1), institute
The fluorination leaching agent stated is fluorine-containing containing ammonium circulation reagent, [F-] concentration be 5~20mol/L,
[NH4 +]/[F-] molar ratio be 0~1, pH value be -1~7, pH value react [H+] concentration, determine that the leaching of titaniferous materials is anti-
Speed is answered, determines leaching efficiency；If fluorine-containing containing [F in ammonium circulation reagent-] concentration and when pH value not up to standard, the HF recycled with process
Supplement；[NH4 +] concentration deficiency when with process recycle NH3Supplement.
3. according to claim 1 produce TiO with rutile ore2The method of powder, which is characterized in that in step (1), institute
The leaching process stated, solid-to-liquid ratio are 10~200g/L, and extraction temperature is at 20~160 DEG C, and extraction time is in 10~180min.
4. according to claim 1 produce TiO with rutile ore2The method of powder, which is characterized in that in step (2), institute
The pyrohydrolysis temperature stated is 200~600 DEG C, and the time is 30~180min.
5. according to claim 1 produce TiO with rutile ore2The method of powder, which is characterized in that in step (3), institute
The impurity removal reagents stated are liquefied ammonia, and the pH value that cleans is between 5.5~9.0, and the temperature that cleans is between 20~100 DEG C, except miscellaneous time is 5
Between~120min.
6. according to claim 1 produce TiO with rutile ore2The method of powder, which is characterized in that in step (3), institute
The course of dissolution stated, solution temperature are 20~100 DEG C, and dissolution time is 5~120min.
7. according to claim 1 produce TiO with rutile ore2The method of powder, which is characterized in that in step (4), institute
The hydrolysing agent stated is liquefied ammonia, hydrolyzes pH value between 7.5~14.0, between 20~100 DEG C, hydrolysis time exists hydrolysis temperature
Between 5~120min.
8. according to claim 1 produce TiO with rutile ore2The method of powder, which is characterized in that in step (5), institute
The pyrohydrolysis temperature stated is 200~600 DEG C, and the time is 30~180min.
9. according to claim 1 produce TiO with rutile ore2The method of powder, which is characterized in that in step (5), institute
The calcining transformation temperature stated is 600~900 DEG C, and the time is 30~180min.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114735747A (en) * | 2022-03-16 | 2022-07-12 | 中南大学 | Method for preparing fluidized chlorination furnace charge by using titanium slag |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109402415A (en) * | 2018-07-17 | 2019-03-01 | 宜宾天原集团股份有限公司 | A kind of preparation of low grade natural rutile can chlorination rich-titanium material method |
| CN109626420A (en) * | 2019-01-15 | 2019-04-16 | 湖南坤泰冶金工程技术有限公司 | A method of titanium dioxide and iron oxide are prepared using fluoride purification ferrotianium material |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109402415A (en) * | 2018-07-17 | 2019-03-01 | 宜宾天原集团股份有限公司 | A kind of preparation of low grade natural rutile can chlorination rich-titanium material method |
| CN109626420A (en) * | 2019-01-15 | 2019-04-16 | 湖南坤泰冶金工程技术有限公司 | A method of titanium dioxide and iron oxide are prepared using fluoride purification ferrotianium material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114735747A (en) * | 2022-03-16 | 2022-07-12 | 中南大学 | Method for preparing fluidized chlorination furnace charge by using titanium slag |
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