CN105621479A - Green preparation technology for TiO2 - Google Patents
Green preparation technology for TiO2 Download PDFInfo
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- CN105621479A CN105621479A CN201610158756.8A CN201610158756A CN105621479A CN 105621479 A CN105621479 A CN 105621479A CN 201610158756 A CN201610158756 A CN 201610158756A CN 105621479 A CN105621479 A CN 105621479A
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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
- C01G23/0536—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing chloride-containing salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/03—Preparation from chlorides
- C01B7/035—Preparation of hydrogen chloride from chlorides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/20—Halides
- C01F11/24—Chlorides
- C01F11/28—Chlorides by chlorination of alkaline-earth metal compounds
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Abstract
The invention relates to a green preparation technology for TiO2. The green preparation technology for TiO2 takes titanium tetrachloride as the raw material and comprises the steps of titanium tetrachloride hydration, hydrogen chloride gas release/titanium-chlorine oxide hydrolysis and precipitation, titanic oxide solid-liquid separation, titanic oxide purification and calcination and hydrogen chloride gas comprehensive utilization. A mother liquor obtained from solid-liquid separation and a washing liquid in the purification process can be used for titanium tetrachloride hydration, the collected hydrogen chloride gas can be absorbed to be used for preparing hydrochloric acid or producing calcium chloride, and the titanic oxide can be processed to obtain high-purity titanium dioxide powder. The green preparation technology for TiO2 has the characteristics of simple flow, fully green process and good TiO2 product quality.
Description
Technical field
The present invention relates to a kind of TiO2Green preparation process.
Background technology
Titanium dioxide is as a kind of important Inorganic Chemicals, have nontoxic, harmless, good chemical stability, thermostability, the dyestuff performance of excellent optics, mechanics and electrical properties and excellence, it is widely used in a lot of field, such as coating, plastics, papermaking, chemical fibre, ink, rubber, electronic industry, makeup, pottery and catalyzer etc. And these application are closely related with particle diameter, brilliant type, degree of crystallinity, the shape looks etc. of titanium dioxide.
The current preparation method about titanium dioxide mainly comprises solid phase method, vapor phase process and liquid phase method; Wherein, liquid phase method is the common method realizing titanium dioxide nano-particle size and morphology controllable. Liquid phase method mainly comprises sol-gel method, sol method, hydrothermal method, solvent-thermal method, electrodip process, microwave method, hydrolysis method etc. In order to obtain the good titanium dioxide of crystallization, then need to prepare at a lower temperature, not only save the energy, it is also possible to reduce titanium dioxide granule and reunite when high-temperature heat treatment. Adding crystal seed is exactly one of method realizing this object at low temperatures. In existing plus seed technique, main employing two kinds of methods preparation hydrolysis plus seeds. One is add in alkali lye generation in titanium tetrachloride aqueous solution and crystal seed, and adds oxalic acid and produce titanium dioxide as auxiliary, and owing to being subject to all multifactor impacts such as system temperature, neutralization speed, the titanium dioxide quality prepared is not good; Two be the nano titanium oxide adding different crystal forms as crystal seed, prepare bigger serface rutile type nano titanic oxide, but overlong time used, it is necessary to crystallization 6��12 days.
In the preparation of existing titanium dioxide, containing a large amount of hydrogenchloride in mother liquor, acidity is very strong, and the crystallization of titanium dioxide or the aftertreatment impact of mother liquor is very big.
Summary of the invention
The technical problem to be solved in the present invention is: based on the problems referred to above, and the present invention provides a kind of TiO2Green preparation process.
The present invention solves the technical scheme that its technical problem adopts: a kind of TiO2Green preparation process, comprise the following steps:
Under agitation, (1) titanium tetrachloride is added in the reactor that hydrated agent is housed, obtains rehydration solution;
(2) raising rehydration solution temperature in reactor, rehydration solution seethes with excitement, and hydrolysis produces titanium oxide precipitation, discharges hydrogen chloride gas simultaneously, collects and reclaim hydrogen chloride gas;
(3) solid-liquid separation, washing titanium oxide precipitation;
(4) dry, calcining, grinding, obtains titania powder.
Further, in step (1), temperature of reaction kettle is-5��120 DEG C, it is preferable that temperature is 0��40 DEG C; The volume ratio of titanium tetrachloride and hydrated agent is 1:1��10, it is preferable that volume ratio is 1:2��5; Hydrated agent is one or more in the mother liquor of pure water, the aqueous solution or the collection of step (3) solid-liquid separation, the filtrate of washing collection.
Further, in step (2), in reactor, feed temperature is 40��120 DEG C, the rehydration solution boiling reaction time > 0.1h.
Further, in step (2), hydrogen chloride gas absorbs through water to prepare hydrochloric acid or absorb through milk of lime and prepares calcium chloride, and hydrogen chloride gas removes pollutent wherein through refining plant process with de-.
Further, in step (3), washing composition is pure water or diluted acid.
Further, in step (4), drying temperature is > 90 DEG C, it is preferable that drying temperature is 110��120 DEG C; Calcining temperature is > 300 DEG C, it is preferable that calcining temperature is 900��1100 DEG C, collects and reclaims the hydrogenchloride of release in drying, calcination process.
In aqueous, the hydrolysis of titanium tetrachloride is a complicated process. Titanium tetrachloride is met water and is first generated solid titanium oxychloride, and under cryogenic, it can rapid aquation be solution state that this solid substance meets water. Along with the rising of temperature, the solution formed after this titanium tetrachloride aquation can occur the hydrolysis reaction of the degree of depth, and then precipitate out solid titanium oxide compound (titanium dioxide/metatitanic acid) and hydrogenchloride.
By utilizing the operational conditions such as temperature, proportioning, pressure, stirring velocity and form can control speed and the degree of hydrolysis reaction, thus regulate hydrogenchloride and the speed of separating out of solid titanium oxide compound, particularly by adding crystal seed or control crystal nucleation situation, the crystalline form of titanium oxide, crystalline size and size distribution can be adjusted. The hydrogenchloride that early stage precipitates out can directly be dissolved in reaction solution, can precipitate out as hydrogen chloride gas after dissolving is saturated from solution. The energy supply (such as keeping solution boiling) continued is conducive to the abundant hydrolysis of titanium oxychloride and the precipitation of titanium oxide and hydrogenchloride in solution, particularly when boiling, hydrogenchloride higher than hydrogenchloride-water azeotrope composition (the normal pressure azeotropic point of hydrogenchloride-water consists of 20.24%, azeotropic point temperature about 108 DEG C) will evaporate from solution.
Utilize the evaporation of reactor and the condensation effect of condenser, continue from still liquid, steam the steam being rich in hydrogenchloride, be liquid by condenser by the water vapor condensation in this steam, thus can resolve and obtain hydrogen chloride gas. In the adition process of titanium tetrachloride, if temperature in the kettle is too high, then on liquid level, the steam partial pressure in gas phase will higher (or saying that this gas phase humidity is bigger), this gas contacts with titanium tetrachloride and hydrolysis reaction and heat release fast will occur, gas turns into Bai Yanzhuan, so that the hydrogen chloride gas precipitated out is polluted. For obtaining clean hydrogen chloride gas, a washing device (such as stuffing washing tower) can be set on the gaseous phase outlet of reactor or respective line, remove the pollutent in this white cigarette shape gas (titanium-containing oxide particulate and acid mist).
Hydrolysis and the brilliant slurry obtained after releasing depressed bundle, can obtain white titanium oxide filter cake after filtration, and this filter cake can use pure water, the acid washing composition such as water, the aqueous solution to carry out carrying out washing treatment. Filter the filtrate obtained and according to its composition situation, the hydrolytic process to rear batch or washing process can be applied mechanically respectively. Filter cake drying and calcining, can obtain solid titanium dioxide. For the particle agglomeration occurred in material after calcining and caking phenomenon, milled processed can be carried out to obtain satisfactory titanium dioxide powder.
The invention has the beneficial effects as follows: the TiO of (1) the present invention2Green preparation process, it is achieved that the full resource utilization of titanium tetrachloride hydrolysis product, the final product of whole process is titanium dioxide, hydrochloric acid/calcium chloride, process green non-pollution; (2) TiO that prepared by the present invention2, what occur in building-up process is the hydrolysis reaction of water and titanium tetrachloride, and synthetic method environmental protection is pollution-free, and can, by the liquid after solid-liquid separation again recycle, be conducive to reducing costs further, protection of the environment; (3) TiO that prepared by the present invention2The method adopted, technological process is controlled, by regulating temperature rise rate to control the rate of release of hydrogenchloride in the precipitation rate of titanium dioxide and hydrolytic process, and can control its grain morphology and particle diameter, obtain good dispersity, the uniform nano-titanium dioxide powder of particle diameter; (4) TiO that prepared by the present invention2The method adopted, simple to operate, temperature of reaction is low, and environmental protection is easy to suitability for industrialized production.
Embodiment
The invention will be further described in conjunction with specific embodiments now, and following examples are intended to the present invention instead of limitation of the invention further are described.
Embodiment 1
Under 200r/min agitation condition, the titanium tetrachloride of 20mL is added drop-wise in the water of 100mL with the speed of 0.5mL/min, drips to add in process and with the speed of 2 DEG C/min, still liquid is extremely seethed with excitement by room temperature simultaneously, finally react 2h when boiling, it is cooled to room temperature, obtains titanium oxide crystalline substance slurry. The hydrogenchloride of release in process, de-except after white suspension particulate through glass spring packing tower, obtain hydrochloric acid by absorbing pure water; Still liquid crystal slurry carries out solid-liquid separation after filtration, and with 0.1% salt acid elution, collects the filtrate in filtration procedure. White filter cake, in 115 DEG C of dry 24h, then calcines 2h in the retort furnace of 500 DEG C, takes out cooling and obtains white titanium dioxide powder.
Embodiment 2
Stir at 400r/min and under cooling conditions, the titanium tetrachloride of 25mL is added drop-wise in the filtrate collected by 100mL embodiment 1 with the speed of 0.8mL/min, drip and add process control still temperature < 40 DEG C, finally obtain clear solution. To keep pressure in still, < 5cm water column, until still liquid seethes with excitement, and maintains 0.5h when boiling, is then cooled to room temperature control heat-up rate, obtains titanium oxide crystalline substance slurry. Hydrolytic process discharges the hydrogenchloride obtained, by absorbing pure water to prepare hydrochloric acid; Still liquid crystal slurry carries out solid-liquid separation after filtration, and with pure water washing, collects the filtrate in filtration procedure. White filter cake, in 200 DEG C of dry 0.5h, then calcines 2h in the retort furnace of 950 DEG C, takes out cooling, obtains Nano titanium dioxide powder after grinding.
Embodiment 3
Under 300r/min agitation condition, in the filtrate that the embodiment 2 that the titanium tetrachloride of 30mL is added drop-wise to 100mL reclaims, drip add process control still temperature < 30 DEG C and control rate of addition to keep < the 3cm water column of pressure in still. Drip and it is warming up to boiling after adding end, and react 1h when boiling, be then cooled to room temperature, obtain titanium oxide crystalline substance slurry. Dripping the hydrogen chloride gas adding release in titanium tetrachloride process is Bai Yanzhuan, takes off except the Titanium oxide particles suspended through 2 grades of concentrated hydrochloric acid bubble cleanings. Hydrolytic process discharges the hydrogenchloride obtained, absorbs with milk of lime and prepare calcium chloride solution. Still liquid crystal slurry carries out solid-liquid separation after filtration, and stream adds pure water gradient wash, collects the filtrate in filtration procedure. White filter cake, in 150 DEG C of dry 0.5h, then calcines 2h in the retort furnace of 1000 DEG C, takes out cooling, obtains Nano titanium dioxide powder after grinding.
Taking the above-mentioned desirable embodiment according to the present invention as enlightenment, by above-mentioned description, relevant staff in the scope not deviateing this invention technological thought, can carry out various change and amendment completely. The content that the technical scope of this invention is not limited on specification sheets, it is necessary to determine its technical scope according to right.
Claims (6)
1. a TiO2Green preparation process, it is characterized in that: comprise the following steps:
Under agitation, (1) titanium tetrachloride is added in the reactor that hydrated agent is housed, obtains rehydration solution;
(2) raising rehydration solution temperature in reactor, rehydration solution seethes with excitement, and hydrolysis produces titanium oxide precipitation, discharges hydrogen chloride gas simultaneously, collects and reclaim hydrogen chloride gas;
(3) solid-liquid separation, washing titanium oxide precipitation;
(4) dry, calcining, grinding, obtains titania powder.
2. a kind of TiO according to claim 12Green preparation process, it is characterized in that: in described step (1), temperature of reaction kettle is-5��120 DEG C, it is preferable that temperature is 0��40 DEG C; The volume ratio of titanium tetrachloride and hydrated agent is 1:1��10, it is preferable that volume ratio is 1:2��5; Hydrated agent is one or more in the mother liquor of pure water, the aqueous solution or the collection of step (3) solid-liquid separation, the filtrate of washing collection.
3. a kind of TiO according to claim 12Green preparation process, it is characterized in that: in described step (2), in reactor, feed temperature is 40��120 DEG C, the rehydration solution boiling reaction time > 0.1h.
4. a kind of TiO according to claim 12Green preparation process, it is characterized in that: in described step (2), hydrogen chloride gas absorbs through water to prepare hydrochloric acid or absorb through milk of lime and prepares calcium chloride, hydrogen chloride gas through refining plant process with de-except pollutent wherein.
5. a kind of TiO according to claim 12Green preparation process, it is characterized in that: in described step (3), washing composition is pure water or diluted acid.
6. a kind of TiO according to claim 12Green preparation process, it is characterized in that: in described step (4) drying temperature for > 90 DEG C, it is preferable that drying temperature is 110��120 DEG C; Calcining temperature is > 300 DEG C, it is preferable that calcining temperature is 900��1100 DEG C, collects and reclaims the hydrogenchloride of release in drying, calcination process.
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| CN201610158756.8A CN105621479A (en) | 2016-03-18 | 2016-03-18 | Green preparation technology for TiO2 |
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| CN201610158756.8A CN105621479A (en) | 2016-03-18 | 2016-03-18 | Green preparation technology for TiO2 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113461049A (en) * | 2021-08-11 | 2021-10-01 | 贵阳精一科技有限公司 | Preparation method of ultrahigh-purity titanium dioxide |
| CN113896233A (en) * | 2020-07-06 | 2022-01-07 | 宁波极微纳新材料科技有限公司 | Method for crystallizing titanium dioxide at low temperature |
| CN113896231A (en) * | 2020-07-06 | 2022-01-07 | 宁波极微纳新材料科技有限公司 | Preparation method of titanium dioxide material |
| CN113896232A (en) * | 2020-07-06 | 2022-01-07 | 宁波极微纳新材料科技有限公司 | Titanium dioxide material and preparation method and application thereof |
| CN113896230A (en) * | 2020-07-06 | 2022-01-07 | 宁波极微纳新材料科技有限公司 | Method for improving dispersibility of titanium dioxide |
| CN115820021A (en) * | 2022-12-06 | 2023-03-21 | 卓芳菲 | Preparation method of anticorrosive, antibacterial and formaldehyde-removing coating |
| CN117088408A (en) * | 2023-10-20 | 2023-11-21 | 西南石油大学 | Nanometer titanium dioxide and preparation method and application thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113896233A (en) * | 2020-07-06 | 2022-01-07 | 宁波极微纳新材料科技有限公司 | Method for crystallizing titanium dioxide at low temperature |
| CN113896231A (en) * | 2020-07-06 | 2022-01-07 | 宁波极微纳新材料科技有限公司 | Preparation method of titanium dioxide material |
| CN113896232A (en) * | 2020-07-06 | 2022-01-07 | 宁波极微纳新材料科技有限公司 | Titanium dioxide material and preparation method and application thereof |
| CN113896230A (en) * | 2020-07-06 | 2022-01-07 | 宁波极微纳新材料科技有限公司 | Method for improving dispersibility of titanium dioxide |
| CN113896232B (en) * | 2020-07-06 | 2023-09-22 | 宁波极微纳新材料科技有限公司 | Titanium dioxide material and preparation method and application thereof |
| CN113896231B (en) * | 2020-07-06 | 2023-09-29 | 宁波极微纳新材料科技有限公司 | Preparation method of titanium dioxide material |
| CN113896230B (en) * | 2020-07-06 | 2024-02-06 | 极微纳(福建)新材料科技有限公司 | Method for improving dispersibility of titanium dioxide |
| CN113896233B (en) * | 2020-07-06 | 2024-02-09 | 极微纳(福建)新材料科技有限公司 | Method for crystallizing titanium dioxide at low temperature |
| CN113461049A (en) * | 2021-08-11 | 2021-10-01 | 贵阳精一科技有限公司 | Preparation method of ultrahigh-purity titanium dioxide |
| CN115820021A (en) * | 2022-12-06 | 2023-03-21 | 卓芳菲 | Preparation method of anticorrosive, antibacterial and formaldehyde-removing coating |
| CN117088408A (en) * | 2023-10-20 | 2023-11-21 | 西南石油大学 | Nanometer titanium dioxide and preparation method and application thereof |
| CN117088408B (en) * | 2023-10-20 | 2023-12-26 | 西南石油大学 | Nanometer titanium dioxide and preparation method and application thereof |
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Application publication date: 20160601 |