CN101255288A - Nano titanium oxide inorganic surface treatment method - Google Patents
Nano titanium oxide inorganic surface treatment method Download PDFInfo
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- CN101255288A CN101255288A CNA2007101906901A CN200710190690A CN101255288A CN 101255288 A CN101255288 A CN 101255288A CN A2007101906901 A CNA2007101906901 A CN A2007101906901A CN 200710190690 A CN200710190690 A CN 200710190690A CN 101255288 A CN101255288 A CN 101255288A
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Abstract
The invention discloses a nm titanium dioxide inorganic surface treating method. The inorganic surface treating is performed when the nm titanium dioxide is in good dispersed state and the inorganic surface treatment effect is increased using the said method. The invention solves the flocculation and dispersion problem of nm titanium dioxide using ultrasonic field, mechanical agitation and film separation and phase integrating. During the process of treating the inorganic surface, on the one hand the nm titanium dioxide dispersion liquid is always under the action of mechanical agitation and ultrasonic, on the other hand, the impurity ions are continuously removed using membrane separation device, so as to make sure the inorganic surface coating reaction under the full dispersed state of the nm titanium dioxide.
Description
Technical field
The present invention relates to a kind of powder inorganic surface treating method, more specifically to a kind of nano titanium oxide inorganic surface treatment method.
Background technology
Nano titanium oxide is a kind of novel inorganic functional materials, is widely used in fields such as shielding ultraviolet rays, changeable colors along with angle coating, opto-electronic conversion, photochemical catalysis.Titanium dioxide is a kind of N-type semiconductor, when wavelength during less than the uviolizing titanium dioxide of 400nm, electronics on the valence band can absorb ultraviolet ray and be excited on the conduction band, produce electron-hole pair simultaneously, the surface is moved to meeting in portions of electronics-hole, cause the hydroxyl and the planar water of titanium dioxide surface to produce hydroxyl free radical, hydroxyl free radical has very strong oxidation capacity, and its oxidation operation is on every side decomposed.Because the particle diameter of nano titanium oxide is little, hole and electronics reduced the probability of hole and electronics recombine, thereby nano titanium oxide have higher photocatalytic activity from the time shortening of crystals arrival plane of crystal.Nano titanium oxide adds in the organic systems such as makeup, plastics, rubber, chemical fibre, coating, under the irradiation of light, very easily causes organic medium degraded on every side and variable color.Therefore, for strengthening the light stability of nano titanium oxide, need carry out inorganic surfaces to it and handle.It is to be nucleome with the nano-titania particle that inorganic surfaces is handled, and by element doping or surface densification coating, sets up barrier at nano-titania particle between surrounding medium, thereby improves the light stability of nano titanium oxide.
At present, the nano titanium oxide inorganic process of surface treatment is at first to carry out handling at inorganic surfaces, and then carries out solid-liquid separation and the foreign ion of washing to produce except that dereaction.In traditional nano titanium oxide inorganic process of surface treatment process, there are a large amount of foreign ions in reaction system, these foreign ions can make, and the dispersive nano-titania particle flocculates again, form the bigger aggregate of particle diameter, cause a large amount of inorganic coatings to be deposited in the nano titanium oxide reunion collective, influence the effect that inorganic surfaces is handled.In addition, general both at home and abroad employing mechanical stirring is guaranteed dispersing nanometer titanium dioxide in the inorganic surfaces treating processes.But because nano-titania particle is little, specific surface area is big, surface energy is high, be in the energy unsure state, be easy to flock together and form coacervate, pure mechanical dispersion can't guarantee that nano titanium oxide is carrying out inorganic surfaces all the time and coating under abundant dispersive state.For example: Chinese patent CN 1454939A proposes the nano titanium dioxide paste liquid that makes is heated to 60-69 ℃, under the state that stirs, drips sodium aluminate solution and sulphuric acid soln simultaneously, at the nano titanium oxide surface-coated aluminum oxide.Chinese patent CN 1067967C proposes a kind of superfine titanium white surface cladding tech and reactor thereof, this technology is wrapped silicon at first add sodium silicate solution and sulphuric acid soln in titanium dioxide slurries, and then adds sodium hydroxide and Tai-Ace S 150 is finished the alclad process.Above-mentioned patent does not all take measures to alleviate flocculation and the agglomeration traits in the nano titanium oxide inorganic surface treatment process.
Summary of the invention
The purpose of this invention is to provide a kind of nano titanium oxide inorganic surface treatment method, this method has overcome the shortcoming that exists in the existing method, existing problems of the prior art have been solved, use this kind method and can make nano-titania particle under good dispersion state, carry out the inorganic surfaces processing, improve the inorganic surfaces treatment effect.
The present invention is achieved by the following technical solutions:
Nano titanium oxide inorganic surface treatment method of the present invention may further comprise the steps:
(1) at first in deionized water, adds dispersion agent, add nano titanium oxide then, utilize dispersing apparatus to prepare nano titanium dioxide water-dispersion liquid;
(2) nano titanium dioxide water-dispersion liquid is joined in the inorganic surfaces treatment reactor, add deionized water, be diluted to that the nano titanium oxide quality accounts for 4%～12% of quality in the dispersion liquid, open mechanical stirring device and ultrasonic dispersing device on the reactor, the dispersion liquid temperature is risen to 40～95 ℃, and the pH value of regulating nano titanium oxide dispersion is 8～10;
(3) in reactor, add respectively and a kind ofly be acid inorganic surfaces treatment solution and a kind ofly be alkaline inorganic surfaces treatment solution, the pH value of keeping nano titanium oxide dispersion is 8～10, the reactant quality accounts for 3～30% of quality in the inorganic surfaces treatment solution, chemical reaction takes place and can form inorganic coating in two kinds of treatment solutions in reactor, inorganic coating accounts for 5%～30% of titanium dioxide quality;
(4) when flocculation takes place in the nano titanium oxide in the reactor, temporarily stopping inorganic surfaces handling, open feed pump, nano titanium dioxide paste hydraulic pressure is gone into membrane separation unit, the partial impurities ion that the inorganic surfaces processing reaction produces sees through the micropore of film with filtrate, and discharge in the mode of cross-flow, nano titanium dioxide paste body after concentrating returns the inorganic surfaces treatment reactor after membrane separation unit flows out, the nano titanium oxide quality accounts for 4%～12% of quality in the reactor to keep simultaneously to add deionized water in reactor, material is circulation repeatedly between reactor and membrane separation unit, and the foreign ion that produces in the inorganic surfaces treating processes is constantly removed;
(5) when the specific conductivity of filtrate during less than 300 μ S/cm, repeating step (3) operation is proceeded inorganic surfaces and is handled; When flocculation took place the nano titanium oxide in the reactor, then repeating step (4) operation was removed foreign ion by membrane separation unit; That is: when flocculation takes place the nano titanium oxide in the reactor, stop inorganic surfaces and handle, open membrane separation unit and remove foreign ion, when the specific conductivity of filtrate less than 300 μ S/cm, close membrane separation unit, proceed inorganic surfaces and handle, so repeatable operation;
(6) after the inorganic surfaces treatment solution adds, continue stirring, ultra-sonic dispersion 10～60min, regulating the pH value then is 6.0～8.0, continues stirring, ultra-sonic dispersion 10～60min again;
(7) nano titanium dioxide paste liquid is constantly washed by membrane separation unit, add deionized water simultaneously, keep that the quality of nano titanium oxide accounts for 4%～12% of quality in the reactor; When the specific conductivity of discharging filtrate during less than 200 μ S/cm, stop to add deionized water, nano titanium oxide dispersion is concentrated to the nano titanium oxide quality accounts for 15%～25% of quality, after drying, the pulverizing, obtain the nano-titanium dioxide powder product of handling through inorganic surfaces.
In nano titanium oxide inorganic surface treatment method of the present invention, described dispersion agent is to be preferably a kind of in Sodium hexametaphosphate 99, tripoly phosphate sodium STPP, trisodium phosphate, sodium polyacrylate and the ammonium polyacrylate, and the dispersion agent quality accounts for 0.5%～1.5% of titanium dioxide quality; Describedly be acid inorganic surfaces treatment solution and be preferably in inorganic acid aqueous solution, aluminum saline solution and the zirconium saline solution one or more; Describedly be alkaline inorganic surfaces treatment solution and be preferably in aqueous silicate solution, the aluminate aqueous solution and the inorganic base aqueous solution one or more; Used separatory membrane is preferably mineral membrane or organic membrane in the described membrane separation unit.
In nano titanium oxide inorganic surface treatment method of the present invention, described mineral acid is more preferably sulfuric acid, nitric acid, hydrochloric acid or phosphoric acid again; Described aluminium salt is more preferably Tai-Ace S 150, aluminum chloride or aluminum nitrate again; Described zirconates is more preferably zirconium sulfate or basic zirconium chloride again; Described silicate is more preferably water glass or potassium silicate again; Described aluminate is sodium metaaluminate more preferably again; Described mineral alkali is more preferably sodium hydroxide, potassium hydroxide, ammoniacal liquor, yellow soda ash or salt of wormwood again.
The present invention adopts the mutually integrated method of ultrasonic field, mechanical stirring and membrane sepn to solve the flocculation and the scattering problem of nano titanium oxide in the inorganic surfaces treating processes.In the inorganic surfaces treating processes, nano titanium oxide dispersion is under mechanical stirring and the action of ultrasonic waves always on the one hand, utilize membrane separation unit will react the foreign ion that produces on the other hand and constantly remove, guarantee that nano-titania particle is fully carrying out the inorganic surfaces coating reaction under the dispersive state all the time.
Advantage of the present invention is: (1) utilizes membrane separation unit in time the foreign ion that the inorganic surfaces processing reaction produces to be removed, and has effectively avoided ion pair nano-titania particle throwing out; (2) ultrasonic energy produces cavatition, and generation speed is about 110ms
-1Microjet, make liquid be in the HF oscillation state simultaneously; Utilize action of ultrasonic waves can make nano-titania particle be in good dispersion state, alleviate the agglomeration between nano-titania particle, simultaneously can the accelerated reaction thing in the mixing and the reaction of micro-scale; (3) mechanical stirring in the inorganic surfaces treating processes can make that feed liquid is in good macroscopic motion state in the reactor, guarantees that feed liquid mixes on macro-size; (4) with membrane separation unit, mechanical stirring, ultrasonic dispersing and the integrated method of inorganic surfaces processing reaction, nanoparticle dispersion, inorganic surfaces processing and the isolating combination of foreign ion have been realized, improved quality product, little, the good light stability of the aggregate particle size of products obtained therefrom.
Description of drawings
Accompanying drawing is a nano titanium oxide inorganic surface treatment method technical process schematic block diagram of the present invention.Wherein: the 1st, the nano titanium oxide diverting device; The 2nd, inorganic surface treatment agent solution basin; The 3rd, pH regulator agent basin; The 4th, the deionized water basin; The 5th, the ultrasonic dispersing device; The 6th, mechanical stirring device; The 7th, the inorganic surfaces treatment reactor; The 8th, feed pump; The 9th, under meter; The 10th, membrane separation unit; The 11st, spray-dryer; The 12nd, micronizer mill; V1～V8 is a control valve.
Embodiment
Below by specific embodiment explanation the present invention, but the present invention not merely is defined in these embodiment.
As shown in the figure: nano titanium oxide process diverting device 1 is dispersed into the aqueous dispersions of single particle state, enters in the inorganic surfaces treatment reactor 7 by control valve V1.The ultrasonic wave that provides mechanical stirring and ultrasonic dispersing device 5 to produce by mechanical stirring device 6 makes the nano titanium oxide in the reactor be in good dispersion state.Inorganic surface treatment agent and pH regulator agent enter inorganic surfaces treatment reactor 7 by inorganic surface treatment agent solution basin 2 and pH regulator agent basin 3 respectively, by the pH value of control valve V2, V3 control input speed and adjusting material.The nano titanium dioxide paste body is pressed into membrane separation unit 10 by control valve V5 by feed pump 8 in the inorganic surfaces treatment reactor 7, and the flow of nano titanium dioxide paste body is controlled jointly by control valve V6 and under meter 9.Foreign ion in the nano titanium dioxide paste body is discharged with filtrate by control valve V7 behind membrane sepn.The nano titanium dioxide paste body that is concentrated turns back to inorganic surfaces treatment reactor 7 again, and the deionized water in the deionized water basin 4 is constant substantially with the solid content of keeping nano titanium oxide in the reactor through control valve V4 adding inorganic surfaces treatment reactor.Material is circulation repeatedly between reactor and membrane separation unit, and the foreign ion that the inorganic surfaces treating processes produces is constantly removed.After the inorganic surfaces processing finishes, utilize specific conductivity that membrane separation unit 10 washs nano titanium dioxide paste liquid filtrate less than 200 μ S/cm, and then nano titanium oxide dispersion is concentrated to certain solid content.By feed pump 8 nano titanium oxide dispersion is pressed into spray-dryer 11 through control valve V8 and carries out drying, after after micronizer mill 12 pulverizing, obtain the nano-titanium dioxide powder product of handling through inorganic surfaces.
In 210 kilograms of deionized waters, add 0.4 kilogram of Sodium hexametaphosphate 99 as dispersion agent, after the Sodium hexametaphosphate 99 dissolving, add 80 kilograms of rutile type nano titanic oxides (median size 30 nanometers) again, be mixed with the nano titanium dioxide paste body, the pH value of regulating slurries with aqueous sodium hydroxide solution is 9.5.The nano titanium dioxide paste body of gained is placed diverting device 1 (PM-PMC270 sand mill), and the zirconia ball that with the diameter is 0.8-1.0mm grinds and disperses 120min as grinding medium, makes nano titanium dioxide water-dispersion liquid.Nano titanium dioxide water-dispersion liquid enters by control valve V1 in 2000 liters the inorganic surfaces treatment reactor 7, adds deionized water, and being diluted to solid content is 12%.Opening mechanical stirring device 6 and ultrasonic dispersing device 5 makes the nano titanium oxide in the reactor be in good dispersion state.Open heating system and make that the temperature of nano titanium dioxide water-dispersion liquid rises to 90 ℃ in the reactor.Be that massfraction is 10% sodium silicate aqueous solution in the inorganic surface treatment agent solution basin 2, quality is 380 kilograms, is that massfraction is 5% dilute sulphuric acid in the pH regulator agent basin 3.Open control valve V2, V3, add sodium silicate aqueous solution and dilute sulphuric acid respectively to inorganic surfaces treatment reactor 7, the pH value of controlling input speed and adjusting nano titanium oxide dispersion by control valve V2, V3 is 9.0～10.0.When flocculation took place the nano titanium oxide in the reactor, closed control valve V2, V3 stopped inorganic surfaces and handle.Opening controlling valve V5 and feed pump 8 are pressed into membrane separation unit 10 with the nano titanium dioxide paste body, and the flow of nano titanium dioxide paste body is controlled jointly by control valve V6 and under meter 9.Foreign ion in the nano titanium dioxide paste body is discharged by control valve V7 behind membrane sepn.The nano titanium dioxide paste body that is concentrated turns back to inorganic surfaces treatment reactor 7 again, and the deionized water in the deionized water basin 4 is constant substantially with the solid content of keeping nano titanium oxide in the reactor through control valve V4 adding reactor.Material is circulation repeatedly between reactor and membrane separation unit, and the foreign ion that the inorganic surfaces treating processes produces is constantly removed.The specific conductivity of discharging filtrate as control valve V7 is closed feed pump 8, control valve V4, V5 less than 300 μ S/cm, opens control valve V2, V3, proceeds inorganic surfaces and handles.Like this: when flocculation takes place the nano titanium oxide in the reactor, stopping inorganic surfaces handling, open membrane separation unit 10 and remove foreign ion, when control valve V7 discharges the specific conductivity of filtrate less than 300 μ S/cm, close membrane separation unit 10, proceed inorganic surfaces and handle, so repeatable operation.After sodium silicate aqueous solution added, closed control valve V3 continued stirring, ultra-sonic dispersion 10min, opens control valve V3 then, adds sulfuric acid, and regulating the pH value is 8.0, and continuation is stirred, ultra-sonic dispersion 60min, the end of inorganic surfaces processing reaction.Opening controlling valve V5 and feed pump 8 constantly wash nano titanium dioxide paste liquid by membrane separation unit 10, open control valve V4 simultaneously and add deionized water, and the solid content of keeping nano titanium oxide in the reactor is constant substantially.The specific conductivity of discharging filtrate as control valve V7 is during less than 200 μ S/cm, closed control valve V4, and it is 25% that nano titanium oxide dispersion is concentrated to solid content.Open control valve V8, closed control valve V6 is pressed into spray-dryer 11 to the nano titanium oxide concentrated solution and carries out spraying drying, carries out comminution by gas stream by micronizer mill 12 at last, obtains the nano-titanium dioxide powder product of handling through the silicon oxide inorganic surfaces.
In 210 kilograms of deionized waters, add 0.6 kilogram of Sodium hexametaphosphate 99 as dispersion agent, after the Sodium hexametaphosphate 99 dissolving, add 60 kilograms of anatase-type nanometer titanium dioxides (median size 10 nanometers) again, be mixed with the nano titanium dioxide paste body, the pH value of regulating slurries with aqueous sodium hydroxide solution is 9.0.The nano titanium dioxide paste body of gained is placed diverting device 1 (PM-PMC270 sand mill), and the zirconia ball that with the diameter is 0.8-1.0mm grinds and disperses 120min as grinding medium, makes nano titanium dioxide water-dispersion liquid.Nano titanium dioxide water-dispersion liquid enters by control valve V1 in 2000 liters the inorganic surfaces treatment reactor 7, adds deionized water, and being diluted to solid content is 4%.Opening mechanical stirring device 6 and ultrasonic dispersing device 5 makes the nano titanium oxide in the reactor be in good dispersion state.Open heating system and make that the temperature of nano titanium dioxide water-dispersion liquid rises to 70 ℃ in the reactor.Be that massfraction is 15% aluminum sulfate aqueous solution in the inorganic surface treatment agent solution basin 2, quality is 523 kilograms; Be that massfraction is 5% aqueous sodium hydroxide solution in the pH regulator agent basin 3.Open control valve V2, V3, add aluminum sulfate aqueous solution and aqueous sodium hydroxide solution respectively in reactor, the pH value of controlling input speed and adjusting nano titanium oxide dispersion by control valve V2, V3 is 8.0～9.0.When flocculation took place the nano titanium oxide in the reactor, closed control valve V2, V3 stopped inorganic surfaces and handle.Opening controlling valve V5 and feed pump 8 are pressed into membrane separation unit 10 with the nano titanium dioxide paste body, and the flow of nano titanium dioxide paste body is controlled jointly by control valve V6 and under meter 9.Foreign ion in the nano titanium dioxide paste body is discharged by V7 after membrane separation unit separates.The nano titanium dioxide paste body that is concentrated turns back to the inorganic surfaces treatment reactor again, and the deionized water in the deionized water basin 4 is constant substantially with the solid content of keeping nano titanium oxide in the reactor through control valve V4 adding reactor.Material is circulation repeatedly between reactor and membrane separation unit, and the foreign ion that the inorganic surfaces treating processes produces is constantly removed.The specific conductivity of discharging filtrate as control valve V7 is closed feed pump 8, control valve V4, V5 less than 300 μ S/cm, opens control valve V2, V3, proceeds inorganic surfaces and handles.Like this: when flocculation takes place the nano titanium oxide in the reactor, stop inorganic surfaces and handle, open membrane separation unit 10 and remove foreign ion, when control valve V7 discharges the specific conductivity of filtrate less than 300 μ S/cm, close membrane separation unit, proceed inorganic surfaces and handle, so repeatable operation.After aluminum sulfate aqueous solution added, closed control valve V3 continued stirring, ultra-sonic dispersion 30min.Adding massfraction and be 5% dilute sulphuric acid, to regulate pH value be 6.0, continues to stir, ultra-sonic dispersion 30min the end of inorganic surfaces processing reaction.Opening controlling valve V5 and feed pump 8 constantly wash nano titanium dioxide paste liquid by membrane separation unit, open control valve V4 simultaneously and add deionized water, and the solid content of keeping nano titanium oxide in the reactor is constant substantially.The specific conductivity of discharging filtrate as control valve V7 is during less than 200 μ S/cm, closed control valve V4, and it is 10% that nano titanium oxide dispersion is concentrated to solid content.Open control valve V8, closed control valve V6 is pressed into spray-dryer 11 to the nano titanium oxide concentrated solution and carries out spraying drying, carries out comminution by gas stream by micronizer mill 12 at last, obtains the nano-titanium dioxide powder product of handling through the aluminium hydroxide inorganic surfaces.
In 210 kilograms of deionized waters, add 0.72 kilogram of Sodium hexametaphosphate 99 as dispersion agent, after the Sodium hexametaphosphate 99 dissolving, add 72 kilograms of rutile type nano titanic oxides (median size 15 nanometers) again, be mixed with the nano titanium dioxide paste body, the pH value of regulating slurries with aqueous sodium hydroxide solution is 9.0.The nano titanium dioxide paste body of gained is placed diverting device 1 (PM-PMC270 sand mill), and the zirconia ball that with the diameter is 0.8-1.0mm grinds and disperses 120min as grinding medium, makes nano titanium dioxide water-dispersion liquid.Nano titanium dioxide water-dispersion liquid enters by control valve V1 in 2000 liters the inorganic surfaces treatment reactor 7, adds deionized water, and being diluted to solid content is 6%.Opening mechanical stirring device 6 and ultrasonic dispersing device 5 makes the nano titanium oxide in the reactor be in good dispersion state.Open heating system and make that the temperature of nano titanium dioxide water-dispersion liquid rises to 40 ℃ in the reactor.Be that massfraction is 8.3% sodium aluminate aqueous solution in the inorganic surface treatment agent solution basin 2, quality is 140 kilograms; Be that massfraction is 5% phosphate aqueous solution in the pH regulator agent basin 3.Open control valve V2, V3, add sodium aluminate aqueous solution and phosphate aqueous solution respectively in reactor, the pH value of controlling input speed and adjusting nano titanium oxide dispersion by control valve V2, V3 is 8.5～9.5.When flocculation took place the nano titanium oxide in the reactor, closed control valve V2, V3 stopped inorganic surfaces and handle.Opening controlling valve V5 and feed pump 8 are pressed into membrane separation unit 10 with the nano titanium dioxide paste body, and the flow of nano titanium dioxide paste body is controlled jointly by control valve V6 and under meter 9.Foreign ion in the nano titanium dioxide paste body is discharged by control valve V7 after membrane separation unit separates.The nano titanium dioxide paste body that is concentrated turns back to the inorganic surfaces treatment reactor again, and the deionized water in the deionized water basin 4 is constant substantially with the solid content of keeping nano titanium oxide in the reactor through control valve V4 adding reactor.Material is circulation repeatedly between reactor and membrane separation unit, and the foreign ion that the inorganic surfaces treating processes produces is constantly removed.The specific conductivity of discharging filtrate as control valve V7 is closed feed pump 8, control valve V4, V5 less than 300 μ S/cm, opens control valve V2, V3, proceeds inorganic surfaces and handles.Like this: when flocculation takes place the nano titanium oxide in the reactor, stop inorganic surfaces and handle, open membrane separation unit and remove foreign ion, when control valve V7 discharges the specific conductivity of filtrate less than 300 μ S/cm, close membrane separation unit, proceed inorganic surfaces and handle, so repeatable operation.After sodium aluminate aqueous solution added, closed control valve V3 continued stirring, ultra-sonic dispersion 60min, opens control valve V3 then, adds phosphate aqueous solution, and regulating the pH value is 7.0, restir, ultra-sonic dispersion 10min, and the inorganic surfaces processing reaction finishes.Opening controlling valve V5 and feed pump 8 constantly wash nano titanium dioxide paste liquid by membrane separation unit, open control valve V4 simultaneously and add deionized water, and the solid content of keeping nano titanium oxide in the reactor is constant substantially.The specific conductivity of discharging filtrate as control valve V7 is during less than 200 μ S/cm, closed control valve V4, and it is 20% that nano titanium oxide dispersion is concentrated to solid content.Open control valve V8, closed control valve V6 is pressed into spray-dryer 11 to the nano titanium oxide concentrated solution and carries out spraying drying, carries out comminution by gas stream by micronizer mill 12 at last, obtains the nano-titanium dioxide powder product of handling through the aluminum phosphate inorganic surfaces.
Comparative Examples 1
In 210 kilograms of deionized waters, add 0.4 kilogram of Sodium hexametaphosphate 99 as dispersion agent, after the Sodium hexametaphosphate 99 dissolving, add 80 kilograms of rutile type nano titanic oxides (median size 30 nanometers) again, be mixed with the nano titanium dioxide paste body, the pH value of regulating slurries with sodium hydroxide solution is 9.5.The nano titanium dioxide paste body of gained is placed diverting device 1 (PM-PMC270 sand mill), and the zirconia ball that with the diameter is 0.8-1.0mm grinds 120min as grinding medium, makes nano titanium dioxide water-dispersion liquid.Nano titanium dioxide water-dispersion liquid enters by control valve V1 in 2000 liters the inorganic surfaces treatment reactor 7, adds deionized water, and being diluted to solid content is 12%.Opening mechanical stirring device 6 and ultrasonic dispersing device 5 makes the nano titanium oxide in the reactor be in good dispersion state.Open heating system and make that the temperature of nano titanium dioxide water-dispersion liquid rises to 90 ℃ in the reactor.Be that massfraction is 10% sodium silicate aqueous solution in the inorganic surface treatment agent solution basin 2, quality is 380 kilograms; Be that massfraction is 5% dilute sulphuric acid in the pH regulator agent basin 3.Open control valve V2, V3, add sodium silicate aqueous solution and dilute sulphuric acid respectively in reactor, the pH value of controlling input speed and adjusting nano titanium dioxide paste liquid by control valve V2, V3 is 9.0～10.0.After sodium silicate aqueous solution added, closed control valve V3 continued stirring, ultra-sonic dispersion 10min, opens control valve V3 then, adds sulfuric acid, and regulating the pH value is 8.0, and continuation is stirred, ultra-sonic dispersion 60min, the end of inorganic surfaces processing reaction.Opening controlling valve V5 and feed pump 8 constantly wash nano titanium dioxide paste liquid by membrane separation unit, open control valve V4 simultaneously and add deionized water, and the solid content of keeping nano titanium oxide in the reactor is constant substantially.The specific conductivity of discharging filtrate as control valve V7 is during less than 200 μ S/cm, closed control valve V4, and it is 25% that nano titanium oxide dispersion is concentrated to solid content.Open control valve V8, closed control valve V6 is pressed into spray-dryer 11 to the nano titanium oxide concentrated solution and carries out spraying drying, carries out comminution by gas stream by micronizer mill 12 at last, obtains the nano-titanium dioxide powder product of handling through the silicon oxide inorganic surfaces.
Comparative Examples 2
In the Comparative Examples 2, except that not using the dispersion of ultrasonic dispersing device, other operation is all identical with embodiment 1.
Comparative Examples 3
In 210 kilograms of deionized waters, add 0.6 kilogram of Sodium hexametaphosphate 99 as dispersion agent, after the Sodium hexametaphosphate 99 dissolving, add 60 kilograms of anatase-type nanometer titanium dioxides (median size 10 nanometers) again, be mixed with the nano titanium dioxide paste body, the pH value of regulating slurries with sodium hydroxide solution is 9.0.The nano titanium dioxide paste body of gained is placed diverting device 1 (PM-PMC270 sand mill), and the zirconia ball that with the diameter is 0.8-1.0mm grinds and disperses 120min as grinding medium, makes nano titanium dioxide water-dispersion liquid.Nano titanium dioxide water-dispersion liquid enters by control valve V1 in 2000 liters the inorganic surfaces treatment reactor 7, adds deionized water, and being diluted to solid content is 4%.Opening mechanical stirring device 6 and ultrasonic dispersing device 5 makes the nano titanium oxide in the reactor be in good dispersion state.Open heating system and make that the temperature of nano titanium dioxide water-dispersion liquid rises to 70 ℃ in the reactor.Be that massfraction is 15% aluminum sulfate aqueous solution in the inorganic surface treatment agent solution basin 2, quality is 523 kilograms; Be that massfraction is 5% aqueous sodium hydroxide solution in the pH regulator agent basin 3.Open control valve V2, V3, add aluminum sulfate aqueous solution and aqueous sodium hydroxide solution respectively in reactor, the pH value of controlling input speed and adjusting nano titanium dioxide paste liquid by control valve V2, V3 is 8.0～9.0.After aluminum sulfate aqueous solution added, closed control valve V3 continued stirring, ultra-sonic dispersion 30min; Adding massfraction and be 5% dilute sulphuric acid, to regulate pH value be 6.0, continues to stir, ultra-sonic dispersion 30min the end of inorganic surfaces processing reaction.Opening controlling valve V5 and feed pump 8 constantly wash nano titanium dioxide paste liquid by membrane separation unit, open control valve V4 simultaneously and add deionized water, and the solid content of keeping nano titanium oxide in the reactor is constant substantially.The specific conductivity of discharging filtrate as control valve V7 is during less than 200 μ S/cm, closed control valve V4, and it is 10% that nano titanium oxide dispersion is concentrated to solid content.Open control valve V8, closed control valve V6 is pressed into spray-dryer 11 to the nano titanium oxide concentrated solution and carries out spraying drying, carries out comminution by gas stream by micronizer mill 12 at last, obtains the nano-titanium dioxide powder product of handling through the aluminium hydroxide inorganic surfaces.
Comparative Examples 4
In the Comparative Examples 4, except that not using the dispersion of ultrasonic dispersing device, other operation is all identical with embodiment 2.
Comparative Examples 5
In 210 kilograms of deionized waters, add 0.72 kilogram of Sodium hexametaphosphate 99 as dispersion agent, after the Sodium hexametaphosphate 99 dissolving, add 72 kilograms of rutile type nano titanic oxides (median size 15 nanometers) again, be mixed with the nano titanium dioxide paste body, the pH value of regulating slurries with sodium hydroxide solution is 9.0.The nano titanium dioxide paste body of gained is placed diverting device 1 (PM-PMC270 sand mill), and the zirconia ball that with the diameter is 0.8-1.0mm grinds and disperses 120min as grinding medium, makes nano titanium dioxide water-dispersion liquid.Nano titanium dioxide water-dispersion liquid enters by control valve V1 in 2000 liters the inorganic surfaces treatment reactor 7, adds deionized water, and being diluted to solid content is 6%.Opening mechanical stirring device 6 and ultrasonic dispersing device 5 makes the nano titanium oxide in the reactor be in good dispersion state.Open heating system and make that the temperature of nano titanium dioxide water-dispersion liquid rises to 40 ℃ in the reactor.Be that massfraction is 8.3% sodium aluminate aqueous solution in the inorganic surface treatment agent solution basin 2, quality is 140 kilograms; Be that massfraction is 5% phosphate aqueous solution in the pH regulator agent basin 3.Open control valve V2, V3, add sodium aluminate aqueous solution and phosphate aqueous solution respectively in reactor, the pH value of controlling input speed and adjusting nano titanium dioxide paste liquid by control valve V2, V3 is 8.5～9.5.After sodium aluminate aqueous solution added, closed control valve V3 continued stirring, ultra-sonic dispersion 60min, opens control valve V3 then, adds phosphate aqueous solution, and regulating the pH value is 7.0, restir, ultra-sonic dispersion 10min, and the inorganic surfaces processing reaction finishes.Opening controlling valve V5 and feed pump 8 constantly wash nano titanium dioxide paste liquid by membrane separation unit, open control valve V4 simultaneously and add deionized water, and the solid content of keeping nano titanium oxide in the reactor is constant substantially.The specific conductivity of discharging filtrate as control valve V7 is during less than 200 μ S/cm, closed control valve V4, and it is 20% that nano titanium oxide dispersion is concentrated to solid content.Open control valve V8, closed control valve V6 is pressed into spray-dryer 11 to the nano titanium oxide concentrated solution and carries out spraying drying, carries out comminution by gas stream by micronizer mill 12 at last, obtains the nano-titanium dioxide powder product of handling through the aluminum phosphate inorganic surfaces.
Comparative Examples 6
In the Comparative Examples 6, except that not using the dispersion of ultrasonic dispersing device, other operation is all identical with embodiment 3.
The mensuration of nano titanium oxide light stability:
Nano titanium oxide after inorganic surfaces handled and 1,3 butylene glycol are that 1: 1 mixed is even by mass ratio, are applied on the slide glass by certain thickness, and covered is surveyed its L, a, b value with the SC80A color difference meter, and aforesaid operations is avoided sunlight as far as possible.Take out after above-mentioned sample panel is placed under the high voltage mercury lamp irradiation 1h, measure L after the illumination with color difference meter again
*, a
*, b
*Be worth, and calculate the value of chromatism Δ E of illumination front and back sample with following formula.
ΔE＝[(L-L
*)
2+(a-a
*)
2+(b-b
*)
2]
1/2。
Wherein L is a lightness dimension, and a and b are tristimulus coordinatess; + a is a red direction, and-a is green direction; + b is yellow direction, and-b is blue look direction.Δ E is big more, and nano-TiO is described
2Photocatalytic activity high more, both light stability was poor more.
Experimental result is as shown in table 1.By table 1 as seen, with respect to the inorganic surface treating method of routine, the good light stability of the nano titanium oxide of gained of the present invention, average aggregate particle size is little, illustrates that inorganic surfaces treatment effect of the present invention is better than ordinary method.
The aberration of table 1 nano titanium oxide and average aggregate particle size
Claims (10)
1, a kind of nano titanium oxide inorganic surface treatment method is characterized in that may further comprise the steps:
(1) at first in deionized water, adds dispersion agent, add nano titanium oxide then, utilize dispersing apparatus to prepare nano titanium dioxide water-dispersion liquid;
(2) nano titanium dioxide water-dispersion liquid is joined in the inorganic surfaces treatment reactor, add deionized water, be diluted to that the nano titanium oxide quality accounts for 4%～12% of quality in the dispersion liquid, open mechanical stirring device and ultrasonic dispersing device on the reactor, the dispersion liquid temperature is risen to 40～95 ℃, and the pH value of regulating nano titanium oxide dispersion is 8～10;
(3) in reactor, add respectively and a kind ofly be acid inorganic surfaces treatment solution and a kind ofly be alkaline inorganic surfaces treatment solution, the pH value of keeping nano titanium oxide dispersion is 8～10, the reactant quality accounts for 3～30% of quality in the inorganic surfaces treatment solution, two kinds of treatment solutions take place to form inorganic coating behind the chemical reaction in reactor, and inorganic coating accounts for 5%～30% of titanium dioxide quality;
(4) when flocculation takes place in the nano titanium oxide in the reactor, temporarily stopping inorganic surfaces handling, open feed pump, nano titanium dioxide paste hydraulic pressure is gone into membrane separation unit, the partial impurities ion that the inorganic surfaces processing reaction produces sees through the micropore of film with filtrate, and discharge in the mode of cross-flow, nano titanium dioxide paste body after concentrating returns the inorganic surfaces treatment reactor after membrane separation unit flows out, the nano titanium oxide quality accounts for 4%～12% of quality in the reactor to keep simultaneously to add deionized water in reactor, material is circulation repeatedly between reactor and membrane separation unit, and the foreign ion that produces in the inorganic surfaces treating processes is constantly removed;
(5) when the specific conductivity of filtrate during less than 300 μ S/cm, repeating step (3) operation is proceeded inorganic surfaces and is handled; When flocculation took place the nano titanium oxide in the reactor, then repeating step (4) operation was removed foreign ion by membrane separation unit;
(6) after the inorganic surfaces treatment solution adds, continue stirring, ultra-sonic dispersion 10～60min, regulating the pH value then is 6.0～8.0, continues stirring, ultra-sonic dispersion 10～60min again;
(7) nano titanium dioxide paste liquid is constantly washed by membrane separation unit, add deionized water simultaneously, keep that the quality of nano titanium oxide accounts for 4%～12% of quality in the reactor; When the specific conductivity of discharging filtrate during less than 200 μ S/cm, stop to add deionized water, nano titanium oxide dispersion is concentrated to the nano titanium oxide quality accounts for 15%～25% of quality, after drying, the pulverizing, obtain the nano-titanium dioxide powder product of handling through inorganic surfaces.
2, nano titanium oxide inorganic surface treatment method according to claim 1, it is characterized in that described dispersion agent is a kind of in Sodium hexametaphosphate 99, tripoly phosphate sodium STPP, trisodium phosphate, sodium polyacrylate and the ammonium polyacrylate, the dispersion agent quality accounts for 0.5%～1.5% of titanium dioxide quality.
3, nano titanium oxide inorganic surface treatment method according to claim 1 is characterized in that described to be acid inorganic surfaces treatment solution be in inorganic acid aqueous solution, aluminum saline solution and the zirconium saline solution one or more; It is described that to be alkaline inorganic surfaces treatment solution be in aqueous silicate solution, the aluminate aqueous solution and the inorganic base aqueous solution one or more.
4, nano titanium oxide inorganic surface treatment method according to claim 1 is characterized in that separatory membrane used in the described membrane separation unit is mineral membrane or organic membrane.
5, nano titanium oxide inorganic surface treatment method according to claim 3 is characterized in that described mineral acid is sulfuric acid, nitric acid, hydrochloric acid or phosphoric acid.
6, nano titanium oxide inorganic surface treatment method according to claim 3 is characterized in that described aluminium salt is Tai-Ace S 150, aluminum chloride or aluminum nitrate.
7, nano titanium oxide inorganic surface treatment method according to claim 3 is characterized in that described zirconates is zirconium sulfate or basic zirconium chloride.
8, nano titanium oxide inorganic surface treatment method according to claim 3 is characterized in that described silicate is water glass or potassium silicate.
9, nano titanium oxide inorganic surface treatment method according to claim 3 is characterized in that described aluminate is a sodium metaaluminate.
10, nano titanium oxide inorganic surface treatment method according to claim 3 is characterized in that described mineral alkali is sodium hydroxide, potassium hydroxide, ammoniacal liquor, yellow soda ash or salt of wormwood.
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