CN108002434A - A kind of method that titanium dioxide is prepared with sulfuric acid - Google Patents
A kind of method that titanium dioxide is prepared with sulfuric acid Download PDFInfo
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- CN108002434A CN108002434A CN201711233718.5A CN201711233718A CN108002434A CN 108002434 A CN108002434 A CN 108002434A CN 201711233718 A CN201711233718 A CN 201711233718A CN 108002434 A CN108002434 A CN 108002434A
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- titanium dioxide
- sulfuric acid
- metatitanic acid
- acid
- metatitanic
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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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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to the manufacture method of titanium dioxide, and in particular to a kind of method that titanium dioxide is prepared with sulfuric acid, carries out slurrying processing, to obtain Titanium dioxide slurry by titanium dioxide base-material；The Titanium dioxide slurry is subjected to decentralized processing, so as to the Titanium dioxide slurry after being disperseed, reaction kettle is under agitation, add 15 35% concentration from sulfuric acid solution, 90 degrees centigrades are preheating to, add metatitanic acid crystal seed, titanous liquid, the titanium dioxide base-material of crushing, and organosilicon, charging are finished, system maintains fluidized state, during titanium dioxide base-material decomposes and metatitanic acid hydrolyzes, concentration of the titanous from 0.3 1.5g/L is kept.After metatitanic acid hydrolyzes, cold filtration, metatitanic acid is separated with mother liquor, using gravity separation stage division, by undecomposed slag separation in metatitanic acid.This law is applicable in the low primary titanium dioxide base-material of trivalent titanium ion content.
Description
Technical field
The present invention relates to field of titanium dioxide production, and in particular to a kind of method that titanium dioxide is prepared with sulfuric acid.
Background technology
Titanium dioxide is acknowledged as Chinese white best now, has splendid optical property, whiteness and covering power, warp
Cross the processing of different surfaces cladding and be widely used in the fields such as coating, plastics, papermaking and ink.In plastic applications, Masterbatch is
More using the amount of titanium dioxide using the more one kind of titanium dioxide, its additive amount can reach more than 70%, so many additive amount,
It is required that titanium dioxide must possess preferable dispersiveness to ensure the easy to process of Masterbatch.On the other hand, due to titanium white powder particles
Surface has photochemical activity point, titanium dioxide is had photocatalysis, and issuing the third contact of a total solar or lunar eclipse in light especially ultraviolet irradiation urges
Change reaction so that the resin degraded dusting being in contact with titanium dioxide, seriously affects the various performances of Masterbatch product and using the longevity
Life.Titanium White Production By Sulfuric Acid Process has the history of last 100 years, is titanium dioxide industrial method earliest, although hydrogenization method in recent years
Production titanium dioxide has faster development, and until current, many countries and regions, particularly China still mainly uses sulfuric acid process
Produce titanium dioxide.Titanium White Production By Sulfuric Acid Process is continuously improved and perfect in long-term practice, and quality is also continuously improved.Sulfuric acid process is given birth to
In the three wastes for producing titanium dioxide, most prominent spent acid mother liquor problem also attracts great attention, and has done substantial amounts of exploratory development work, has had
Spent acid mother liquor fraction is concentrated after return and use, some is produced synthetic rutile, manganese sulfate, phosphorus and is taken using spent acid mother liquor
Larger effect was obtained, but is far from tackling the problem at its root.One ton of titanium dioxide pair fertilizer of production etc., produces 8-10 tons of sulfur acids
Concentration is the spent acid mother liquor of 15-20%, is still the key of Titanium White Production By Sulfuric Acid Process, environment is caused seriously to pollute.Thus,
The method for preparing titanium dioxide has much room for improvement.
The content of the invention
The present invention attempts more thoroughly to solve the problems, such as the spent acid mother liquor of sulfuric acid process, and production link is reduced from technique, subtracts
Few sulfuric acid consumption, reduces production cost.The preparation method of the present invention is such:Titanium dioxide base-material is subjected to slurrying processing, so as to
To Titanium dioxide slurry；The Titanium dioxide slurry is subjected to decentralized processing, so as to the Titanium dioxide slurry after disperse, it is acidproof instead
Under the stirring for answering kettle, the dilute sulfuric acid that free sulphuric acid concentration is 20-30% is added, is preheating to 90 degrees centigrades, adds metatitanic acid
Hydrolysis crystal seed, the reducing agent of trivalent titanium ion solution, the titanium dioxide base-material of crushing, and organosilicon, charging while, constantly raise
Temperature, charging is finished maintains fluidized state by temperature.Titanium dioxide base-material, which is constantly decomposed not cut off the water supply, solves metatitanic acid and sulfuric acid
Ferrous iron, the Fe2O3 in ore deposit are also decomposed and are reduced to ferrous sulfate, and calcium oxide and magnesia also accordingly generate calcium sulfate and sulfuric acid
Magnesium, not for diluted acid decompose mineral such as silica component residue in slag.In whole decomposition and hydrolytic process, three
Valency titanium ion is constantly consumed, and need to be continuously replenished, and must keep trivalent titanium ion 0.3-1.5g/L's in whole reaction process
Concentration, terminates with metatitanic acid hydrolysis completely until titanium dioxide base-material decomposes.Through cold filtration, metatitanic acid and mother liquor point after end
From.Stage division of the metatitanic acid through gravity separation such as hydrocyclone, shale shaking table equipment isolates granularity from metatitanic acid
The slightly larger undecomposed slag of slightly thick proportion, then metatitanic acid through conventional water wash, bleaching, salt treatment, calcining, again through wet-milling, point
Level, surface treatment and drying and crushing preparing titanium dioxide.Reducing agent can use potassium borohydride KBH4, sodium borohydride NaBH4, ethanol
C2H5OH.If the metatitanic acid that reducing agent produced is made using the hydride of titanous, that is, in the presence of hydrogen ion, hydrolysis
The metatitanic acid gone out, under identical salt treatment and calcination condition, can improve the conversion ratio of rutile titanium dioxide, be conducive to make
Take rutile type titanium white.Mother liquor is chilled and isolates the dense of free sulfuric acid when adding initial with the concentrated sulfuric acid after FeSO7H2O
Degree, the concentration of free sulfuric acid when first can also add initial with the concentrated sulfuric acid, then it is chilled and isolate FeSO4 7H2O, filter
Go out limpid dilute circulation as under -- the dilute sulfuric acid of batch preparing titanium dioxide.
Embodiment
Titanium dioxide base-material is subjected to slurrying processing, to obtain Titanium dioxide slurry；The Titanium dioxide slurry is disperseed
Processing, so as to the Titanium dioxide slurry after disperse, under acid-resistant reacting kettle stirring, addition free sulphuric acid concentration 15-35%'s
Dilute sulfuric acid is warming up to 90 degrees centigrades, adds metatitanic acid hydrolysis crystal seed, the reducing agent of trivalent titanium ion, the titanium dioxide through crushing
Base-material, and organosilicon, charging is finished maintains fluidized state by temperature.During sulfuric acid decomposition titanium dioxide base-material at the same time the inclined titanium of hydrolysis
Acid, during titanium dioxide base-material constantly decomposes and metatitanic acid hydrolyzes, reducing agent is constantly consumed.It is necessary in whole process
It is continuously replenished and keeps the presence of micro reducing agent.Finished completely with metatitanic acid hydrolysis when titanium dioxide base-material decomposes, through cooled
Filter separates metatitanic acid with mother liquor.Metatitanic acid using gravity separation stage division by the slightly thick proportion of contained granularity in metatitanic acid slightly
Big undecomposed slag separation comes out, after metatitanic acid through conventional water wash, bleaching, salt treatment, calcining, wet-milling, classification, surface at
Reason, dry, crushing preparing titanium dioxide.
Mother liquor elder generation freezing separation goes out after FeSO47H2O the concentration of free sulfuric acid when adding initial with the concentrated sulfuric acid, can also
The concentration of free sulfuric acid when mother liquor first being added initial with the concentrated sulfuric acid, then freezing and crystallizing isolate FeSO4.7H20, filter out
Limpid dilute sulfuric acid, the dilute sulfuric acid as next group production titanium dioxide.
Signified reducing agent in technique, it is characterized in that referring to the ferrous ion in molten night being reduced to ferric iron immediately
The material of ion, potassium borohydride KBH4, sodium borohydride NaBH4, ethanol C2H5OH.Produced during with the hydride of three titanouses
Metatitanic acid, i.e., the metatitanic acid of hydrolysis in the presence of hydrogen ion, can be corresponding under identical salt treatment and identical calcination condition
Ground improves the conversion ratio of rutile titanium dioxide, is conducive to produce rutile type titanium white.
Claims (4)
- A kind of 1. method that titanium dioxide is prepared with sulfuric acid, it is characterised in that titanium dioxide base-material is subjected to slurrying processing, to obtain Titanium dioxide slurry；The Titanium dioxide slurry is subjected to decentralized processing, so as to the Titanium dioxide slurry after being disperseed, in acid tolerance response Under kettle stirring, the dilute sulfuric acid for adding free sulphuric acid concentration 15-35% is warming up to 90 degrees centigrades, and it is brilliant to add metatitanic acid hydrolysis Kind, the reducing agent of trivalent titanium ion, the titanium dioxide base-material through crushing, and organosilicon, charging is finished maintains fluidized state by temperature. During sulfuric acid decomposition titanium dioxide base-material at the same time hydrolysis metatitanic acid, titanium dioxide base-material constantly decompose and metatitanic acid hydrolysis process In, reducing agent is constantly consumed.It must be continuously replenished in whole process and keep the presence of micro reducing agent.When titanium dioxide base Material decomposes to be finished with metatitanic acid hydrolysis completely, separates metatitanic acid with mother liquor through cold filtration.Metatitanic acid is using gravity separation Stage division comes out the slightly larger undecomposed slag separation of the slightly thick proportion of contained granularity in metatitanic acid, through conventional water after metatitanic acid Wash, bleach, salt treatment, calcining, wet-milling, classification, surface treatment, drying, crush preparing titanium dioxide.
- 2. a kind of method that titanium dioxide is prepared with sulfuric acid as claimed in claim 1, it is characterised in that mother liquor elder generation freezing separation goes out The concentration of free sulfuric acid when adding initial with the concentrated sulfuric acid after FeSO47H2O, first can also add mother liquor with the concentrated sulfuric acid first The concentration of free sulfuric acid during the beginning, then freezing and crystallizing isolate FeSO4.7H20, filter out limpid dilute sulfuric acid, are given birth to as next group Produce the dilute sulfuric acid of titanium dioxide.
- A kind of 3. method that titanium dioxide is prepared with sulfuric acid as claimed in claim 1, it is characterised in that signified reduction in technique Agent, it is characterized in that refer to the ferrous ion in molten night being reduced to the material of ferric ion immediately, potassium borohydride KBH4, Sodium borohydride NaBH4, ethanol C2H5OH.The metatitanic acid produced during with the hydride of three titanouses, i.e., in the presence of hydrogen ion The metatitanic acid of hydrolysis, under identical salt treatment and identical calcination condition, can correspondingly improve rutile titanium dioxide Conversion ratio, be conducive to produce rutile type titanium white.
- A kind of 4. method that titanium dioxide is prepared with sulfuric acid as claimed in claim 1, it is characterised in that signified gravity in technique Preparation equipment, separates the slightly larger undecomposed slag of the slightly thick proportion of granularity in metatitanic acid it is characterized in that referring to, as eccentricity separates Device.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711233718.5A CN108002434A (en) | 2017-11-30 | 2017-11-30 | A kind of method that titanium dioxide is prepared with sulfuric acid |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114956168A (en) * | 2022-07-07 | 2022-08-30 | 华东理工大学 | Method for producing titanium dioxide through continuous hydrolysis |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1217298A (en) * | 1998-02-24 | 1999-05-26 | 广州市华昌科技开发有限公司 | Preparation of titanic-schorl type titanium white by hydrochloric -acid process |
| CN1613776A (en) * | 2003-11-04 | 2005-05-11 | 谢亚汉 | Preparation for titanium pigment with sulfuric acid circulating use |
-
2017
- 2017-11-30 CN CN201711233718.5A patent/CN108002434A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1217298A (en) * | 1998-02-24 | 1999-05-26 | 广州市华昌科技开发有限公司 | Preparation of titanic-schorl type titanium white by hydrochloric -acid process |
| CN1613776A (en) * | 2003-11-04 | 2005-05-11 | 谢亚汉 | Preparation for titanium pigment with sulfuric acid circulating use |
Non-Patent Citations (1)
| Title |
|---|
| 李化全: "硫酸法钛白粉生产中杂质3价铁的新型去除法", 《化工生产与技术》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114956168A (en) * | 2022-07-07 | 2022-08-30 | 华东理工大学 | Method for producing titanium dioxide through continuous hydrolysis |
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