CN104477987B - A kind of clean preparation method of high-purity titanium dioxide - Google Patents
A kind of clean preparation method of high-purity titanium dioxide Download PDFInfo
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Abstract
The invention provides a kind of clean preparation method of high-purity titanium dioxide, described method with rich titanium material for raw material, rich titanium material is obtained by reacting sodium titanate intermediate with sodium hydroxide under hydrothermal conditions, then described sodium titanate intermediate washing is obtained metatitanic acid, again described metatitanic acid is carried out ammonia and soak reaction, standing for the product after reacting, filtration, oven dry and calcining are prepared high-purity titanium dioxide.Described method can realize ferrotianium and be separated, the rich titanium material of more than 95% is converted into the high-purity titanium dioxide of purity more than 99.5%, and achieve the recycle of sodium hydroxide, ammoniacal liquor and water, greatly reduce raw-material consumption, reaching the object of cleaner production, is the simple and novel method preparing high-purity titanium dioxide that technical process is short of a kind of technical feasibility, equipment.
Description
Technical field
The invention belongs to preparation and the Mineral resources processing technique field of mineral compound, particularly relate to a kind of clean preparation method of high-purity titanium dioxide.
Background technology
High-purity Ti O
2refer to TiO
2purity is the TiO of 99.3%-99.9%
2, be mainly used in that luxury food medicine, makeup, chemical analysis are pure, reagent type and electronic industry etc.Due to high-purity Ti O
2there is semiconducting behavior, and specific inductivity and resistivity higher, in China, high-purity Ti O
2be one of new electronic component principal crystalline phase raw material, be widely used in higfh-tension ceramics electric capacity, MLCC, semicoductor capacitor, semiconductive ceramic and piezoelectric ceramics etc.
High-purity Ti O
2main preparation methods have sulfuric acid process, TiCl
4direct hydrolysis method, chlorination process and Titanium alkoxides hydrolysis method etc., existing domestic application is mainly sulfuric acid process and TiCl in industrial method
4direct hydrolysis method.
Sulfuric acid process is domestic production pigment-level TiO
2main method, also can prepare high-purity Ti O by the method
2.Its production technique is: the acidolysis of (1) ilmenite (titanium slag), the preparation of sulfate liquor.First the ilmenite of solid (titanium slag) is prepared into the sulfate liquor of soluble titanium with sulfuric acid decomposition, the iron simultaneously in ore deposit (slag) and most of metallic impurity also become the vitriol of solubility, so that separated in operation afterwards; (2) hydrolysis of vitriol, the preparation of hydrated titanium dioxide particle, namely the titanium sulfate solution of black and water react the process that the hydrated titanium dioxide that generates white precipitates, and this process is for preparing high-purity Ti O
2core; (3) calcining of hydrated titanium dioxide, this process be hydrated titanium dioxide at high temperature, through dehydration, desulfurization and transformation of crystal, finally become the high-purity Ti O that there is stable crystalline structure, conform to quality requirements
2product.Sulfuric acid process has the advantages such as relatively not high to titanium material specification of quality, equipment is simple, technical maturity is easily grasped, and therefore, most domestic enterprise adopts this method to produce high-purity Ti O
2.But the sulfate process titanium dioxide technological process of production is long, complex process, often produce 1t titanium white meeting by-product 3 ~ 4t ferrous sulfate, discharge about 20% Waste Sulfuric Acid 7 ~ 11t, acid waste water 100 ~ 250t, waste residue 0.2 ~ 0.3t, serious environment pollution, becomes the bottleneck of titanium powder industry development.
TiCl
4direct hydrolysis method is industrial production high-purity Ti O
2one of main method, its chemical equation is such as formula (1) and formula (2):
TiCl
4+4NaOH→Ti(OH)
4+4NaCl(1)
Ti(OH)
4→TiO
2+2H
2O(2)
The method is TiCl
4hydrolysis generates Ti (OH)
4, Ti (OH)
4calcining generates high-purity Ti O
2product.At TiCl
4in hydrolytic process, to TiCl
4with can add different types of additive in liquid caustic soda reaction system with facilitation of hydrolysis, the kind of additive has tensio-active agent, crystal seed, H
2c
2o
4deng.Adopt the TiO that this method obtains
2product purity is primarily of TiCl
4with the quality control of pure water; The conditional decision of the hydrolysis reaction pattern of product, particle diameter, size distribution; The crystal formation of calcining temperature and time controling product and color.TiCl
4direct hydrolysis method prepares high-purity Ti O
2, due to advantages such as technical process are short, raw material is pure, therefore this method obtains application in enterprise at home.
Chlorination process is one of main method of modern industry production pigmentary titanium dioxide, also can produce high-purity Ti O simultaneously
2, this technological process is natural rutile ore deposit (artificial rutile or titanium slag)) and under the existence of reductive agent (coke or refinery coke), generate thick TiCl through high-temp chlorination
4, thick TiCl
4pure smart TiCl is obtained through distilation
4; Essence TiCl
4in oxidation reactor, gaseous oxidation generates high-purity Ti O
2.Chlorination process has the advantages such as technical process is short, good product quality, automatic controlling level are high, " three wastes " quantity discharged is few, and the pigmentary titanium dioxide of the world 57% output all adopts this method to produce, but concentrates in several large enterprises of more American-European developed countries; Because chlorination process technical difficulty is comparatively large, high to titanium material specification of quality, equipment material requires harsh, Jinzhou titanium industry in domestic enterprise, is only had to adopt chlorination process production pigmentary titanium dioxide, but not with this method industrial production high-purity Ti O
2.
Titanium alkoxides hydrolysis method is also prepare high-purity Ti O
2one of method.First this technique be the synthesis of Titanium alkoxides, under the effect of ammonia, and TiCl
4with alcohols material, as ethanol, butanols, isopropanol reaction generate Titanium alkoxides; Be the hydrolysis of Titanium alkoxides again, the same with titanium hydrolysis in sulfuric acid process, Titanium alkoxides in case of heating, obtains metatitanic acid after hydrolysis; Finally, metatitanic acid calcines the high-purity Ti O obtaining certain crystal formation at a certain temperature
2.The material purity that this technique adopts is higher, pure introducing in preparation process, and the characteristic utilizing alcohols material be hydrolyzed, prepares that purity is higher, particle diameter is suitable for, the more uniform high-purity Ti O of size-grade distribution
2product, process repeatability is better, and quality product is more stable.But the alcohols materials such as this technical process is longer, and subsidiary material price is higher, ethanol, solvent oil, ammonia etc. are combustiblesubstance or poisonous, in preparation process, Safety production questions is very outstanding, and cost is high, therefore in modern industry is produced, this method is not also adopted to produce high-purity Ti O
2.
Patent CN100542968C discloses a kind of method utilizing sodium hydroxide clean production of titanium dioxide, the method take titanium slag as raw material, react at 350 ~ 550 DEG C and sodium hydroxide and obtain intermediate product, then anatase titanium dioxide or rutile titanium dioxide is prepared after carrying out intermediate product washing (or carbonating), acid-soluble, reduction, hydrolysis and calcining, but because institute's iron content enters solid phase with sodium titanate in titanium slag, cause a difficult problem for ferrotianium sepn process complexity; Patent CN101190802B discloses a kind of clean preparation method of titanium slag preparing rutile-type titanium dioxide by hydrothermal method, the method take titanium slag as raw material, utilize sodium hydroxide hydrothermal method to obtain sodium titanate intermediate, then intermediate is separated and directly prepare rutile titanium dioxide through being hydrolyzed again.This invention utilizes simple technique to prepare rutile TiO
2, but also there is the problem of ferrotianium sepn process complexity, therefore urgently research and develop a kind of method realizing ferrotianium high efficiency separation, patent CN102030367A discloses a kind of preparation method of high-purity titanium dioxide, and the method is reacted after titanium tetrachloride hydrolysis with oxalic acid, and oxalic oxygen titanium, roasting obtains high-purity Ti O
2, but the method has higher requirements to titanium tetrachloride purity, and must more than 99%, patent CN1156690A discloses a kind of manufacture method of rutile type high-purity titanium dioxide, the method adopts special sulfuric acid process to carry out acidolysis, leaching reduction, sedimentation filtration Crystallization Separation, the techniques such as hydrolysed filtrate washing drying and calcining pulverizing and special auxiliary agent are made, but production technique is comparatively complicated, in addition, patent CN101993242A discloses a kind of ultra-fine lead titanate, lead barium titanate ceramic powder and preparation method thereof, the method is included in reactor and first adds a certain amount of metatitanic acid, then excessive alkali (as strong aqua) is added, add appropriate strong oxidizer hydrogen peroxide (hydrogen peroxide) again, it is made to dissolve completely (and the pH value of regulator solution is 8 ~ 14), then equimolar lead ion or lead ion is added, the mixing solutions of barium ion, obtain flocculent deposit, after abundant stirring reaction, suction filtration washing precipitation (useful surface-active agents dipping 1 ~ 2 time), dry precipitation again, within 1 ~ 10 hour, lead titanate can be obtained 700 DEG C of calcinings, lead barium titanate ultrafine powder.But the object of the method is preparation ultra-fine lead titanate, lead barium titanate ceramic powder, is not yet applied to separating titanium and iron.
Summary of the invention
The object of the present invention is to provide a kind of clean preparation method of high-purity titanium dioxide, the method can realize ferrotianium and be separated, be high-purity titanium dioxide by rich titanium material Efficient Conversion under the condition that temperature is lower, and achieve alkali circulation and ammonia circulation, greatly reduce raw-material consumption.
For reaching this object, the present invention by the following technical solutions:
A clean preparation method for high-purity titanium dioxide, comprises the following steps:
(1) hydro-thermal reaction: rich titanium material is mixed with sodium hydroxide (NaOH) solution, carries out hydro-thermal reaction, the material after reaction is carried out solid-liquor separation, and gained solid phase is hydro-thermal material;
(2) washing makes the transition: described hydro-thermal material is added to the water washing, and carries out solid-liquor separation, and gained solid phase is washing material transition;
(3) ammonia leaching reaction: described washing material transition is carried out ammonia leaching reaction, and the product after reaction is carried out solid-liquor separation, gained liquid phase is ammonia leaching solution;
(4) gel is separated out: left standstill by described ammonia leaching solution, carry out solid-liquor separation when there is gel in described ammonia leaching solution, gained solid phase dried;
(5) calcine: oven dry solid phase step (4) obtained is pulverized, and calcining obtains high-purity high-purity titanium dioxide (TiO
2) powder.
The clean preparation method of high-purity titanium dioxide provided by the invention is for raw material with rich titanium material, it is obtained by reacting sodium titanate intermediate (hydro-thermal material) under hydrothermal conditions with sodium hydroxide, then the washing of sodium titanate intermediate is obtained metatitanic acid (washing material transition), under ammoniacal liquor and hydrogen peroxide effect, carry out ammonia leaching reaction again, in ammonia leaching reaction, impure metatitanic acid can generate pertitanic acid ammonium (NH with ammoniacal liquor selective reaction
4)
2tiO
3nH
2o enters solution, and impurity stays solid phase, and under 15 ~ 40 DEG C of static conditions, pertitanic acid ammonium divides and parses yellow gel hydrous titanium oxide, obtains high-purity titanium dioxide through solid-liquor separation, oven dry and calcining.
Rich titanium material of the present invention is known raw material, and those skilled in the art can obtain easily.Various raw material of the present invention all obtains easily by being purchased or preparing voluntarily, and described each equipment is this area common equipment.
In described step (1), the concentration of sodium hydroxide solution is 300 ~ 500g/L, as 320g/L, 350g/L, 380g/L, 400g/L, 420g/L, 450g/L, 470g/L or 490g/L, the mass ratio (alkali ore deposit ratio) of sodium hydroxide and rich titanium material is 2 ~ 5:1, as 2.2:1,2.5:1,2.7:1,3.0:1,3.5:1,3.8:1,4.0:1,4.2:1,4.5:1 or 4.8:1; Hydrothermal temperature is 130 ~ 240 DEG C, as 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 195 DEG C, 200 DEG C, 210 DEG C, 230 DEG C or 235 DEG C, the hydro-thermal reaction time is 1 ~ 5h, as 1.5h, 2.0h, 2.5h, 3.0h, 3.5h, 4.0h or 4.5h, the stirring velocity of hydro-thermal reaction is 300 ~ 600r/min, as 320r/min, 350r/min, 370r/min, 390r/min, 400r/min, 450r/min, 500r/min, 520r/min, 550r/min or 580r/min; Described hydro-thermal reaction is carried out in autoclave; The liquid phase that described solid-liquor separation obtains is for alternative sodium hydroxide solution.
In described step (2), the volume mL of water is 2 ~ 10:1 with the ratio of the quality g of hydro-thermal material, if 3:1,3.5:1,4:1,4.5:1,5:1,5.5:1,6:1,6.5:1,7:1,7.5:1,8:1,8.5:1,9:1 or 9.5:1 wash temperature is 10 ~ 40 DEG C, as 15 DEG C, 20 DEG C, 25 DEG C, 30 DEG C, 35 DEG C or 38 DEG C, washing time is 10 ~ 60min, as 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min or 58min.In described step (2), gained solid phase is washing material transition, for containing small amounts iron (Fe
2o
3) metatitanic acid or metatitanic acid, gained liquid phase is sodium hydroxide solution that is siliceous, aluminium, gained liquid phase through removal of impurities, evaporation enrichment after return step (1) continue use.
In described step (3), ammonia leaching reaction is specially: mixed with pure water by described washing material transition, add ammoniacal liquor and hydrogen peroxide wherein; The make the transition ratio of quality g of material of the volume mL of described pure water and washing is 2 ~ 4:1, as 2.3:1,2.5:1,2.7:1,2.9:1,3.0:1,3.2:1,3.5:1,3.7:1 or 3.9:1; Quality g: the volume mL of ammoniacal liquor of washing material transition: the volume mL of hydrogen peroxide is 1:3 ~ 8:4 ~ 16, as 1:3.5:15,1:4:4.5,1:5.5:5,1:5.5:6,1:6:14,1:6.5:7,1:7:7.5,1:7.5:8,1:7.5:9,1:7.5:10,1:7.5:11,1:6:13 or 1:3.5:12; The temperature of described ammonia leaching reaction is 0 ~ 5 DEG C, as 0.5 DEG C, 1 DEG C, 1.5 DEG C, 2 DEG C, 2.5 DEG C, 3 DEG C, 3.5 DEG C, 4 DEG C or 4.5 DEG C; The time of described ammonia leaching reaction is 10 ~ 60min, as 15min, 20min, 25min, 28min, 32min, 35min, 38,40min, 45min, 50min, 55min or 58min.As preferred technical scheme, in described step (3) pure water and washing make the transition material stir on magnetic stirring apparatus obtain uniform suspension after in ice-water bath, carry out ammonia again with ammoniacal liquor and hydrogen peroxide soak and react.Described hydrogen peroxide and ammoniacal liquor can add simultaneously also can successively add.After ammonia leaching reaction, the solid phase that solid-liquor separation obtains is the impurity phase of iron content etc., and liquid phase is the clear yellow-green colour ammonia leaching solution of titaniferous, achieves ferrotianium and is separated.
The temperature that in described step (4), ammonia leaching solution leaves standstill is 15 ~ 40 DEG C, as 20 DEG C, 22 DEG C, 25 DEG C, 28 DEG C, 30 DEG C, 35 DEG C or 38 DEG C, the time left standstill is 2 ~ 8h, as 2.5h, 3.0h, 3.5h, 4.0h, 4.5h, 5.0h, 5.5h, 6.0h, 6.5h, 7.0h or 7.5h, the pertitanic acid ammonium generated due to ammonia leaching reaction can not stable existence and point parse yellow gel hydrous titanium oxide under normal temperature or high temperature, and after the ammonia leaching solution after leaving standstill carries out solid-liquor separation, gained liquid phase returns described step (3) and substitutes pure water.Ammonia leaching solution after leaving standstill can produce yellow gel, after solid-liquor separation, gained solid phase is dried in an oven, bake out temperature is 80 ~ 120 DEG C, as 85 DEG C, 90 DEG C, 95 DEG C, 100 DEG C, 105 DEG C, 110 DEG C, 105 DEG C or 108 DEG C, drying time is 3 ~ 6h, as 3.5h, 4.0h, 4.2h, 4.5h, 4.8h, 5.0h, 5.2h, 5.5h or 5.8h, obtains yellow solid particle after oven dry.
Step (5) described calcining is carried out in retort furnace, before calcining, described oven dry solid phase is crushed to below 20 orders, described calcining temperature is 500 ~ 700 DEG C, as 520 DEG C, 550 DEG C, 580 DEG C, 600 DEG C, 620 DEG C, 650 DEG C or 680 DEG C, this calcining temperature is conducive to the generation of anatase titania, calcination time is 2 ~ 3h, as 2.2h, 2.5h or 2.8h.
Compared with prior art, beneficial effect of the present invention is:
1, the clean preparation method technique of high-purity titanium dioxide provided by the invention is simple, achieves the high efficiency separation of titanium and other impurity in rich titanium material under cryogenic: in rich titanium material, the transformation efficiency of titanium is more than 95%, gained anatase titanium dioxide TiO
2purity more than 99.5%;
2, the clean preparation method of high-purity titanium dioxide provided by the invention achieves the recycle of sodium hydroxide solution, ammoniacal liquor and water, greatly reduces raw-material consumption, reaches the object of cleaner production;
3, the clean preparation method of high-purity titanium dioxide provided by the invention is owing to adopting hydro-thermal reaction, and rich titanium material and sodium hydroxide therefore can be made under cryogenic to react, and compared with traditional sulfuric acid process, avoids sour consumption high, refuse and the shortcoming such as by product is many; Compared with chlorination process, stable reaction, temperature of reaction reduces more than 800 DEG C, greatly reduces energy consumption;
4, the novel method preparing high-purity titanium dioxide that the clean preparation method of high-purity titanium dioxide provided by the invention is a kind of technical feasibility, equipment is simple, technical process is short.
Accompanying drawing explanation
Fig. 1 is the process flow sheet preparing high-purity titanium dioxide provided by the invention.
Embodiment
Technical scheme of the present invention is further illustrated by embodiment below in conjunction with accompanying drawing.
Be illustrated in figure 1 the process flow sheet preparing high-purity titanium dioxide provided by the invention, as can be seen from the figure, described technique mainly comprises the following steps:
(1) hydro-thermal reaction: rich titanium material is mixed with sodium hydroxide solution, carries out hydro-thermal reaction, the material after reaction is carried out solid-liquor separation, and gained solid phase is hydro-thermal material, and gained liquid phase is sodium hydroxide circulation fluid;
(2) washing makes the transition: described hydro-thermal material is added to the water washing, and carries out solid-liquor separation, and gained solid phase is washing material transition, and gained liquid phase returns step (1) after treatment and continues use;
(3) ammonia leaching reaction: mixed with pure water by described washing material transition, add ammoniacal liquor and hydrogen peroxide wherein, carry out ammonia leaching reaction, and the product after reaction is carried out solid-liquor separation, gained liquid phase is ammonia leaching solution;
(4) gel is separated out: left standstill by described ammonia leaching solution, carry out solid-liquor separation when there is gel in described ammonia leaching solution, gained solid phase is dried, and gained liquid phase returns described step (3) and substitutes pure water;
(5) calcine: oven dry solid phase step (4) obtained is pulverized, and calcining obtains high-purity titanium dioxide powder.
The composition of rich titanium material used in the embodiment of the present invention is: TiO
281.57%, Fe
2o
337%, SiO
20.38%, Al
2o
30.57%, rich titanium material grain graininess is below 75 μm.Rich titanium material composition also can be other concrete content, and rich titanium material composition can not be used for limiting the scope of the invention.
Embodiment 1
(1) rich titanium material hydro-thermal reaction: preparation 400g/LNaOH solution 400mL, rich titanium material 40g is taken than 4:1 by setting alkali ore deposit, add after mixing in autoclave and carry out hydro-thermal reaction at 200 DEG C, stirring velocity is 400r/min, slurry is taken out after reaction 1h, solid-liquor separation, obtains hydro-thermal material and NaOH circulation fluid;
(2) washing makes the transition: after step (1) terminates, hydro-thermal material is added to the water, be 5:1 by the ratio of wash water volume (mL) and hydro-thermal quality of material (g), 30min is washed at 25 DEG C, realize the washing transition of material, solid-liquor separation after washing makes the transition, solid phase is washing material transition, for containing a small amount of Fe
2o
3metatitanic acid or metatitanic acid, liquid phase is sodium hydroxide solution that is siliceous, aluminium, this sodium hydroxide solution through removal of impurities, evaporation enrichment after return step (1);
(3) ammonia leaching reaction: after step (2) terminates, pressing and forming the volume of water (mL) of metatitanic acid unit for uniform suspension with the ratio of the quality (g) of metatitanic acid is 2:1, get 10g washing material transition to mix with 20mL pure water, be placed on magnetic stirring apparatus and stir, move in ice-water bath after forming unit for uniform suspension, by metatitanic acid (g): ammoniacal liquor (mL): the ratio of hydrogen peroxide (mL) is that 1:3:4 adds a certain amount of hydrogen peroxide and ammoniacal liquor in described unit for uniform suspension, ammonia leaching reaction is carried out at 0 DEG C, after reaction 10min, the product obtained is carried out solid-liquor separation, solid phase after solid-liquor separation is the impurity phases such as iron, liquid phase is the clear yellow-green colour ammonia leaching solution of titaniferous,
(4) gel is separated out: after step (3) terminates, the yellow-green colour titaniferous solution obtained is left standstill 2h at 15 DEG C, obtain yellow gel, the solid phase obtained after solid-liquor separation is placed in baking oven and is heated to 80 DEG C of oven dry 4h, obtain yellow solid particle, liquid phase can return step (3) and substitute pure water;
(5) calcine: after step (4) terminates, in retort furnace, calcine 3h in 550 DEG C after yellow solid granular powder being broken into the following particle of 60 order, just obtain the pure high-purity Ti O of white
2powder.
Analyze through chemistry titration Ti or ICP-OES, recording titanium transformation efficiency is 97.2%, the Detitanium-ore-type TiO obtained
2purity is 99.2%.
Embodiment 2
(1) rich titanium material hydro-thermal reaction: preparation 500g/LNaOH solution 400mL, rich titanium material 40g is taken than 5:1 by setting alkali ore deposit, add after mixing in autoclave and carry out hydro-thermal reaction at 220 DEG C, stirring velocity is 500r/min, slurry is taken out after reaction 5h, solid-liquor separation, obtains hydro-thermal material and NaOH circulation fluid;
(2) washing makes the transition: after step (1) terminates, hydro-thermal material is added to the water, be 8:1 by the ratio of wash water volume (mL) and hydro-thermal quality of material (g), 60min is washed at 10 DEG C, realize the washing transition of material, carry out solid-liquor separation after washing transition, solid phase is washing material transition, for containing a small amount of Fe
2o
3metatitanic acid or metatitanic acid, liquid phase is sodium hydroxide solution that is siliceous, aluminium, this sodium hydroxide solution through removal of impurities, evaporation enrichment after return step (1);
(3) ammonia leaching reaction: after step (2) terminates, the volume mass ratio pressing water and the metatitanic acid forming metatitanic acid unit for uniform suspension is 3:1, after getting 10g washing transition, material mixing with 30mL pure water, be placed on magnetic stirring apparatus and stir, move in ice-water bath after forming unit for uniform suspension, by metatitanic acid (g): ammoniacal liquor (mL): the ratio of hydrogen peroxide (mL) is that 1:4:6 adds a certain amount of hydrogen peroxide and ammoniacal liquor in described unit for uniform suspension, ammonia leaching reaction is carried out at 5 DEG C, after reaction 20min, the slurry obtained is carried out solid-liquor separation, solid phase after solid-liquor separation is the impurity phases such as iron, liquid phase is the clear yellow-green colour ammonia leaching solution of titaniferous,
(4) gel is separated out: after step (3) terminates, the yellow-green colour titaniferous solution obtained is left standstill 5h at 30 DEG C, obtain yellow gel, the solid phase obtained after solid-liquor separation is placed in baking oven and is heated to 120 DEG C of oven dry 5h, obtain yellow solid particle, liquid phase can return step (3) and substitute pure water;
(5) calcine: after step (d) terminates, in retort furnace, calcine 3h in 650 DEG C after yellow solid granular powder being broken into the following particle of 80 order, just obtain the pure high-purity Ti O of white
2powder.
Analyze through chemistry titration Ti or ICP-OES, recording titanium transformation efficiency is 95.3%, the Detitanium-ore-type TiO obtained
2powder purity is 99.3%.
Embodiment 3
(1) rich titanium material hydro-thermal reaction: preparation 300g/LNaOH solution 400mL, rich titanium material 40g is taken than 3:1 by setting alkali ore deposit, add after mixing in autoclave and carry out hydro-thermal reaction at 220 DEG C, stirring velocity is 300r/min, slurry is taken out after reaction 4h, solid-liquor separation, obtains hydro-thermal material and NaOH circulation fluid;
(2) washing makes the transition: after step (1) terminates, hydro-thermal material is added to the water, be 2:1 by the ratio of wash water volume (mL) and hydro-thermal quality of material (g), 30min is washed at 25 DEG C, realize the washing transition of material, solid-liquor separation after washing makes the transition, solid phase is washing material transition, for containing a small amount of Fe
2o
3metatitanic acid or metatitanic acid, liquid phase is sodium hydroxide solution that is siliceous, aluminium, this sodium hydroxide solution through removal of impurities, evaporation enrichment after return step (1);
(3) ammonia leaching reaction: after step (2) terminates, the volume mass ratio pressing water and the metatitanic acid forming metatitanic acid unit for uniform suspension is 4:1, after getting 10g washing transition, material mixing with 40mL pure water, be placed on magnetic stirring apparatus and stir, move in ice-water bath after forming unit for uniform suspension, by metatitanic acid (g): ammoniacal liquor (mL): the ratio of hydrogen peroxide (mL) is that 1:8:16 adds a certain amount of hydrogen peroxide and ammoniacal liquor in described unit for uniform suspension, ammonia leaching reaction is carried out at 3 DEG C, after reaction 60min, the slurry obtained is carried out solid-liquor separation, solid phase after solid-liquor separation is the impurity phases such as iron, liquid phase is the clear yellow-green colour ammonia leaching solution of titaniferous,
(4) gel is separated out: after step (3) terminates, the yellow-green colour titaniferous solution obtained is left standstill 6h at 35 DEG C, obtain yellow gel, the solid phase obtained after solid-liquor separation is placed in baking oven and is heated to 90 DEG C of oven dry 3h, obtain yellow solid particle, liquid phase can return step (3) and substitute pure water;
(5) calcine: after step (4) terminates, in retort furnace, calcine 3h in 600 DEG C after yellow solid granular powder being broken into the following particle of 20 order, just obtain the pure high-purity Ti O of white
2powder.
Analyze through chemistry titration Ti or ICP-OES, recording titanium transformation efficiency is 95.1%, the Detitanium-ore-type TiO obtained
2purity is 99.5%.
Embodiment 4
(1) rich titanium material hydro-thermal reaction: preparation 300g/LNaOH solution 400mL, rich titanium material 60g is taken than 2:1 by setting alkali ore deposit, add after mixing in autoclave and carry out hydro-thermal reaction at 130 DEG C, stirring velocity is 450r/min, slurry is taken out after reaction 3h, solid-liquor separation, obtains hydro-thermal material and NaOH circulation fluid;
(2) washing makes the transition: after step (1) terminates, hydro-thermal material is added to the water, be 4:1 by the ratio of wash water volume (mL) and hydro-thermal quality of material (g), 10min is washed at 35 DEG C, realize the washing transition of material, solid-liquor separation after washing makes the transition, solid phase is washing material transition, for containing a small amount of Fe
2o
3metatitanic acid or metatitanic acid, liquid phase is sodium hydroxide solution that is siliceous, aluminium, this sodium hydroxide solution through removal of impurities, evaporation enrichment after return step (1);
(3) ammonia leaching reaction: after step (2) terminates, the volume mass ratio pressing water and the metatitanic acid forming metatitanic acid unit for uniform suspension is 2.5:1, after getting 10g washing transition, material mixing with 25mL pure water, be placed on magnetic stirring apparatus and stir, move in ice-water bath after forming unit for uniform suspension, by metatitanic acid (g): ammoniacal liquor (mL): the ratio of hydrogen peroxide (mL) is that 1:6:5 adds a certain amount of hydrogen peroxide and ammoniacal liquor in described unit for uniform suspension, ammonia leaching reaction is carried out at 2 DEG C, after reaction 30min, the slurry obtained is carried out solid-liquor separation, solid phase after solid-liquor separation is the impurity phases such as iron, liquid phase is the clear yellow-green colour ammonia leaching solution of titaniferous,
(4) gel is separated out: after step (3) terminates, the yellow-green colour titaniferous solution obtained is left standstill 8h at 15 DEG C, obtain yellow gel, the solid phase obtained after solid-liquor separation is placed in baking oven and is heated to 100 DEG C of oven dry 4h, obtain yellow solid particle, liquid phase can return step (3) and substitute pure water;
(5) calcine: after step (4) terminates, in retort furnace, calcine 2h in 680 DEG C after yellow solid granular powder being broken into the following particle of 100 order, just obtain the pure high-purity Ti O of white
2powder.
Analyze through chemistry titration Ti or ICP-OES, recording titanium transformation efficiency is 97.4%, the Detitanium-ore-type TiO obtained
2purity is 99.2%.
Embodiment 5
(1) rich titanium material hydro-thermal reaction: preparation 500g/LNaOH solution 400mL, rich titanium material 100g is taken than 2:1 by setting alkali ore deposit, add after mixing in autoclave and carry out hydro-thermal reaction at 240 DEG C, stirring velocity is 600r/min, slurry is taken out after reaction 2h, solid-liquor separation, obtains hydro-thermal material and NaOH circulation fluid;
(2) washing makes the transition: after step (a) terminates, hydro-thermal material is added to the water, be 10:1 by the ratio of wash water volume (mL) and hydro-thermal quality of material (g), 40min is washed at 40 DEG C, realize the washing transition of material, solid-liquor separation after washing makes the transition, solid phase is washing material transition, for containing a small amount of Fe
2o
3metatitanic acid or metatitanic acid, liquid phase is sodium hydroxide solution that is siliceous, aluminium, this sodium hydroxide solution through removal of impurities, evaporation enrichment after return step (a);
(3) ammonia leaching reaction: after step (2) terminates, the volume mass ratio pressing water and the metatitanic acid forming metatitanic acid unit for uniform suspension is 2:1, after getting 10g washing transition, material mixing with 20mL pure water, be placed on magnetic stirring apparatus and stir, move in ice-water bath after forming unit for uniform suspension, by metatitanic acid (g): ammoniacal liquor (mL): the ratio of hydrogen peroxide (mL) is that 1:8:16 adds a certain amount of hydrogen peroxide and ammoniacal liquor in described unit for uniform suspension, ammonia leaching reaction is carried out at 4 DEG C, after reaction 45min, the slurry obtained is carried out solid-liquor separation, solid phase after solid-liquor separation is the impurity phases such as iron, liquid phase is the clear yellow-green colour ammonia leaching solution of titaniferous,
(4) gel is separated out: after step (3) terminates, the yellow-green colour titaniferous solution obtained is left standstill 3h at 40 DEG C, obtain yellow gel, the solid phase obtained after solid-liquor separation is placed in baking oven and is heated to 90 DEG C of oven dry 6h, obtain yellow solid particle, liquid phase can return step (3) and substitute pure water;
(5) calcine: after step (4) terminates, in retort furnace, calcine 2.5h in 580 DEG C after yellow solid granular powder being broken into the following particle of 200 order, obtain the pure high-purity Ti O of white
2powder.
Analyze through chemistry titration Ti or ICP-OES, recording titanium transformation efficiency is 96.7%, the high-purity Ti O obtained
2purity is 99.4%.
Applicant states, the present invention illustrates method detailed of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned method detailed, does not namely mean that the present invention must rely on above-mentioned method detailed and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (21)
1. a clean preparation method for high-purity titanium dioxide, is characterized in that, comprises the following steps:
(1) hydro-thermal reaction: rich titanium material is mixed with sodium hydroxide solution, carries out hydro-thermal reaction, the material after reaction is carried out solid-liquor separation, and gained solid phase is hydro-thermal material;
(2) washing makes the transition: described hydro-thermal material is added to the water washing, and carries out solid-liquor separation, and gained solid phase is washing material transition;
(3) ammonia leaching reaction: described washing material transition is carried out ammonia leaching reaction under the effect of ammoniacal liquor and hydrogen peroxide, described ammonia leaching reaction is carried out under temperature is the condition of 0 ~ 5 DEG C, and the product after reaction is carried out solid-liquor separation, gained liquid phase is ammonia leaching solution;
(4) gel is separated out: left standstill by described ammonia leaching solution, and the temperature that described ammonia leaching solution leaves standstill is 15 ~ 40 DEG C, carries out solid-liquor separation, gained solid phase dried when there is gel in described ammonia leaching solution;
(5) calcine: oven dry solid phase step (4) obtained is pulverized, and calcining obtains high-purity titanium dioxide powder.
2. the clean preparation method of a kind of high-purity titanium dioxide according to claim 1, is characterized in that, described in step (1), the concentration of sodium hydroxide solution is 300 ~ 500g/L, and the mass ratio of sodium hydroxide and rich titanium material is 2 ~ 5:1.
3. the clean preparation method of a kind of high-purity titanium dioxide according to claim 1, is characterized in that, the temperature of step (1) described hydro-thermal reaction is 130 ~ 240 DEG C, and the time of hydro-thermal reaction is 1 ~ 5h.
4. the clean preparation method of a kind of high-purity titanium dioxide according to claim 1, is characterized in that, the stirring velocity of step (1) described hydro-thermal reaction is 300 ~ 600r/min.
5. the clean preparation method of a kind of high-purity titanium dioxide according to claim 1, is characterized in that, the hydro-thermal reaction described in step (1) is carried out in autoclave.
6. the clean preparation method of a kind of high-purity titanium dioxide according to claim 1, is characterized in that, the liquid phase that step (1) described solid-liquor separation obtains is for alternative sodium hydroxide solution.
7. the clean preparation method of a kind of high-purity titanium dioxide according to claim 1, is characterized in that, described in step (2), the volume mL of water is 2 ~ 10:1 with the ratio of the quality g of hydro-thermal material.
8. the clean preparation method of a kind of high-purity titanium dioxide according to claim 1, is characterized in that, the temperature of step (2) described washing is 10 ~ 40 DEG C, and the time of washing is 10 ~ 60min.
9. the clean preparation method of a kind of high-purity titanium dioxide according to claim 1, is characterized in that, after step (2) described solid-liquor separation, gained liquid phase returns step (1) continuation use after removal of impurities and the process of evaporation enrichment.
10. the clean preparation method of a kind of high-purity titanium dioxide according to claim 1, is characterized in that, the leaching of ammonia described in step (3) reaction is specially: mixed with pure water by described washing material transition, add ammoniacal liquor and hydrogen peroxide wherein.
The clean preparation method of 11. a kind of high-purity titanium dioxides according to claim 10, is characterized in that, the make the transition ratio of quality g of material of the volume mL of described pure water and washing is 2 ~ 4:1.
The clean preparation method of 12. a kind of high-purity titanium dioxides according to claim 1, is characterized in that, quality g: the volume mL of ammoniacal liquor of step (3) described washing material transition: the volume mL of hydrogen peroxide is 1:3 ~ 8:4 ~ 16.
The clean preparation method of 13. a kind of high-purity titanium dioxides according to claim 1, is characterized in that, step (3) described ammonia leaching reaction is carried out on magnetic stirring apparatus.
The clean preparation method of 14. a kind of high-purity titanium dioxides according to claim 1, is characterized in that, the leaching reaction times of ammonia described in step (3) is 10 ~ 60min.
The clean preparation method of 15. a kind of high-purity titanium dioxides according to claim 1, is characterized in that, step (3) described ammonia leaching reaction is carried out in ice-water bath.
The clean preparation method of 16. a kind of high-purity titanium dioxides according to claim 1, is characterized in that, the time that ammonia leaching solution described in step (4) leaves standstill is 2 ~ 8h.
The clean preparation method of 17. a kind of high-purity titanium dioxides according to claim 10, is characterized in that, step (4) described solid-liquor separation gained liquid phase returns described step (3) and substitutes pure water.
The clean preparation method of 18. a kind of high-purity titanium dioxides according to claim 1, is characterized in that, the temperature of drying described in step (4) is 80 ~ 120 DEG C, and the time of oven dry is 3 ~ 6h.
The clean preparation method of 19. a kind of high-purity titanium dioxides according to claim 1, is characterized in that, step (4) described oven dry is carried out in an oven.
The clean preparation method of 20. a kind of high-purity titanium dioxides according to claim 1, is characterized in that, described in step (5), the temperature of calcining is 500 ~ 700 DEG C, and the time of described calcining is 2 ~ 3h.
The clean preparation method of 21. a kind of high-purity titanium dioxides according to claim 1, is characterized in that, the described oven dry solid phase of step (5) is crushed to below 20 orders.
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| CN104098133A (en) * | 2014-07-02 | 2014-10-15 | 江苏恒智纳米科技有限公司 | Preparation method for high-efficient photocatalyst-nanometer titanium dioxide water-based colloid |
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