CN105504884B - One kind prepares TiO2The method of/opal composite granule - Google Patents
One kind prepares TiO2The method of/opal composite granule Download PDFInfo
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- CN105504884B CN105504884B CN201410494299.0A CN201410494299A CN105504884B CN 105504884 B CN105504884 B CN 105504884B CN 201410494299 A CN201410494299 A CN 201410494299A CN 105504884 B CN105504884 B CN 105504884B
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Abstract
TiO is prepared the invention discloses one kind2The method of/opal composite granule, this method carries out surface to it modified again by wet type mechanochemical method cladding TiO using ultra-fine opal powder as nuclear material2, obtained TiO2/ opal composite granule cladding is firm, and whiteness is close to pure titanium dioxide, and TiO2Consumption be only prepare TiO2The 20%~40% of/opal composite granule gross weight, and generation environment does not pollute preparation process, the recoverable such as used medium water, dispersant and modifying agent.
Description
Technical field
The invention belongs to technical field of pigment preparation, it is related to a kind of preparation method of pigment, more particularly to one kind prepares TiO2Egg
The method of white stone composite powder material.
Background technology
Titanium dioxide, i.e. pigmentary titanium dioxide, are the optimal inorganic white pigments so far manufactured by people, numerous
Widely apply in field.In recent years, as China builds and the fast development of paint industry and various materials, the need of various titanium dioxide
The amount of asking is growing day by day, but there is the problem of environmental pollutions such as serious waste water,waste gas and industrial residue in production process of titanium pigment but always
It is difficult to solve, and the consumption of the titanium products such as titanium dioxide causes titanium resource increasingly short.These factors result in titanium white production into
This increase, price raises up.Above mentioned problem makes titanium dioxide consumption industry cost gradually increase, and therefore industry development is restricted.
Due to there is presently no inorganic pigment kind of the combination property better than titanium dioxide is developed, preparing and titanium white performance phase
Like and TiO with low cost2/ white mineral composite granule pigment is of problems effective in solving titanium white production and consuming
One of approach.
By inorganic surfaces coating modification mode, in white nonmetal mineral composition granule Surface coating TiO2Layer and formed have
The composite white pigment of TiO 2 pigment property is constantly subjected to concern both domestic and external, and forms mainly anti-with inorganic precipitation
Answer-be heat-treated two kinds of crystallization method and dry conditions grain-grain coating modification method to prepare the technical method of composite pigment.
Wherein, the specific features that inorganic precipitation reacts-be heat-treated crystallization method are：The nonmetallic mineral of matrix will be used as
Grain is placed in the hydrolyzation system of titanium salt (mainly titanyl sulfate), triggers titanium salt hydrolysis, generation hydrated titanium dioxide (TiO2·
H2O mineral particle surface) is covered in, then thermally treated makes the TiO of composite surface2·H2O generation crystal types TiO2Coating thing.
The problem of above method is present mainly has：The inducing action of mineral matter bag core matrix causes hydrated titanium dioxide to precipitate
Thing is difficult to generate rutile titanium dioxide by follow-up crystallization；Restricted, wrapped by titanium salt concentration and solid content in hydrolytic process
Cover TiO2Amount and uniformity coefficient are restricted, and the pigment performance of product is typically up to less than requiring；Titanium salt hydrolyzes miscellaneous with iron ion etc.
The removal of matter produces a large amount of acid waste waters, pollutes environment.
And dry conditions grain-grain coating modification method is by TiO2The machine with dry type percussion is placed in nonmetallic mineral
In tool stirring system, fine grained TiO is realized by the effect such as mechanical dispersion, impact shear2In thicker nonmetallic ore composition granule
The cladding on surface.
But this method, because of nuclear material and TiO2Degree of scatter it is poor, generation is lacked between nuclear material and titanium dioxide firm
Effect excites external force and the binding groups to make the poor performance of composite pigment and unstable.
The country has scholar to be prepared for TiO using natural minerals such as calcium carbonate, sericite, magnesium hydroxide, konilites as core2/
CaCO3Composite white pigment, TiO2/ sericite Chinese white and TiO2/ shepardite composite white pigment.But it is due to that these are white
Color mineral are not acidproof, and in slightly acid application system, the application of these materials is all restricted.
In addition, these do not have cooperative effect as the natural minerals of nuclear material for pigment performance so that the use of titanium dioxide
Measure in more than the 40% of composite granule gross mass could close to pure titanium dioxide performance.
It would therefore be highly desirable to which develop a kind of titanium dioxide consumption approaches covering material during pure titanium dioxide performance, cladding less again
Degree of scatter with nuclear material is good, and the method for preparing titanium dioxide composite granule of the composite granule cladding fastening formed.
The content of the invention
In order to solve the above problems, present inventor has performed studying with keen determination, as a result find：With sodium metasilicate to opal powder
After being handled, the active OH- numbers of opal powder surface are dramatically increased, so that TiO2Powder can be acted in high-speed stirred
Opal powder surface is firmly adsorbed under the shearing force of lower formation, so that solving opal powder belongs to noncrystal,
And be difficult and TiO2The problem of Deng stable coating is formed, so as to complete the present invention.
It is an object of the invention to provide following aspect：
In a first aspect, the present invention, which provides one kind, prepares TiO2The method of/opal composite granule, it is characterised in that the party
Method comprises the following steps：
(1) Sodium Polyacrylate or its solution are added into opal powder, water is added, slurries is made, by albumen stone flour
Body is crushed to d80Particle diameter is 2 μm of ultra-fine opal slurry；
(2) by the ultra-fine opal slurry drying in step (1), ultra-fine opal powder is obtained, then use sodium silicate solution
Surface infiltration processing is carried out to it, then is dried at high temperature, modified superfine opal powder is made, adds water modified superfine egg
Albarium body is configured to modified superfine opal slurries；
(3) by TiO2Powder is mixed with Sodium Polyacrylate or its solution, is stirred, is added water and TiO is made2Slurries；
(4) by obtained modified superfine opal slurries in step (2) and obtained TiO in step (3)2Slurries are mixed,
And solid content in mixed serum is ground to d98Particle diameter is 2 μm, and TiO is made2/ opal composite granule slurries；
(5) by obtained TiO in step (4)2/ opal composite granule slurry dilution, filtering, then filter cake is washed
Wash, finally break up filtration cakes torrefaction.
Second aspect, the present invention above method is also provided, it is characterised in that in step (1), the Sodium Polyacrylate or
The addition of its solution is 0.1wt%~1.5wt% based on opal powder weight in terms of Sodium Polyacrylate weight, is preferably
0.5%~1.2%, such as 1.0%.
The third aspect, the present invention also provides the above method, it is characterised in that in step (1), and the solid content of slurries is made
For 50%~65%, preferably 55%~60%, such as 58%, wherein, the solid content refers to solid content weight and slurry in slurries
The ratio of liquid gross weight.
Fourth aspect, the present invention also provides the above method, it is characterised in that in step (2), the sodium silicate solution
Concentration be 1.0wt%~15.0wt%, more preferably preferably 3.0wt%~12.0wt%, 5.0wt%~10.0wt%, such as
8.0wt%, modulus is 2.0~3.4, preferably 2.4~3.0, such as 2.8.
5th aspect, the present invention also provides the above method, it is characterised in that in step (2), is 80~200 in temperature
DEG C, dried at preferably 100 DEG C~160 DEG C, such as 140 DEG C.
6th aspect, the present invention also provides the above method, it is characterised in that in step (2), the sodium silicate solution
Addition is 2wt%~6wt% based on opal powder weight described in step (1) in terms of sodium metasilicate, preferably 3wt%~
5wt%, such as 4wt%.
7th aspect, the present invention also provides the above method, it is characterised in that in step (2), the modified superfine albumen
The solid content of stone slurries is 50%~65%, preferably 55%~60%, such as 58%, wherein, the solid content refers in slurries
The ratio of solid content weight and slurries gross weight.
Eighth aspect, the present invention above method is also provided, it is characterised in that in step (3), the Sodium Polyacrylate or
The addition of its solution is 0.3wt%~0.8wt% based on opal powder weight in terms of Sodium Polyacrylate, is preferably
0.4wt%~0.6wt%, such as 0.5wt%.
9th aspect, the present invention also provides the above method, it is characterised in that in step (3), the obtained TiO2Slurries
Solid content be 45~55%, preferably 48%~52%, such as 50%, wherein, the solid content refers to solid content weight in slurries
The ratio of amount and slurries gross weight.
Tenth aspect, the present invention also provides the above method, it is characterised in that in step (4), the modified superfine albumen
Stone slurries and TiO2Slurries are according to modified superfine opal powder dry powder weight and TiO2The ratio of powder dry powder weight is modified super
Small protein stone flour soma powder weight:TiO2Powder dry powder weight=1:(4~1.5), preferably 1:(3~2), such as 1:2.5 carry out
Mixing.
A kind of TiO provided according to the present invention2The preparation method of/opal composite powder material, with following beneficial effect
Really：
(1) present invention prepares TiO using mechanochemical method2/ opal composite granule, wherein used WATER AS FLOW MEDIUM,
Dispersant etc. can be reclaimed, reused, and generation environment does not pollute；
(2) preparation TiO2/ opal composite granule method such as only needs to soak, grind and dry at the technique, environmental pollution
It is small；
(3) TiO used in2Itself and non-environmental-pollution, even if there is a small amount of TiO2Pollution is not resulted in into environment yet；
(4) with the obtained TiO2/ opal composite granule moderate in grain size, is suitable for pigment, so as to prevent photocatalysis
Effect；
(5) present invention is simple to operate, and production cost is low, so that pigment price reduction.
Brief description of the drawings
Fig. 1 shows that TiO is made in embodiment 12The scanning electron microscope (SEM) photograph of/opal composite granule；
Fig. 2 shows that TiO is made in embodiment 22The scanning electron microscope (SEM) photograph of/opal composite granule；
Fig. 3 shows that TiO is made in embodiment 32The scanning electron microscope (SEM) photograph of/opal composite granule；
Fig. 4 shows that TiO is made in embodiment 42The scanning electron microscope (SEM) photograph of/opal composite granule；
Fig. 5 shows that the scanning electron microscope (SEM) photograph of product is made in comparative example 1.
Embodiment
Below by the present invention is described in detail, the features and advantages of the invention will become more with these explanations
To be clear, clear and definite.
The present inventor has found by research, in opal Surface coating layer of surface activating agent, improves opal surface and lives
Property, then under dry conditions by the mechanical agitation with percussion by TiO2Albumen stone flour surface is coated on, makes TiO2Can be with
Combined closely by hydrogen bond with opal, form TiO2/ opal composite granule, obtained TiO2/ opal composite granule has
Preferable whiteness, alternative titanium dioxide is used, because it with inexpensive opal is used as nuclear material, therefore, the composite granule
Production cost is reduced, prices, preparation TiO2The method of/opal composite granule is simple to operate, without complex device and
Condition, used medium water can be recycled and reused, and not result in environmental pollution and the waste of the energy.
According to the first aspect of the invention, a kind of TiO is disclosed2The preparation method of/opal composite granule, this method bag
Include following steps：
Step 1, Sodium Polyacrylate or its solution are added to opal powder, adds water, slurries are made, by albumen stone flour
Body is crushed to d80Particle diameter is 2 μm of ultra-fine opal slurry.
Opal, is a kind of natural minerals collection through naturally weathered formation, by main component of amorphous silica
Zoarium, main component is SiO2·nH2O, moisture content 5~10%, because it is amorphous structure, without certain profile, usually
Compact massive, granular, earthy, stalactitic, concretion forms or cellular etc., fracture are conchoidal, and hardness is 5~5.5, in finely divided
State is present, and easily exploits and be processed into powder, and the opal for choosing white is crushed into after albumen stone flour, and its whiteness is up to 90
More than, it is generally used for playing a part of whitening and desalination wrinkle in cosmetics.Its rich reserves, with excellent electric insulation
Property, chemical inertness and good acid-resistant corrosion.
Albumen stone flour used is common commercially available albumen stone flour in the present invention, as Shanghai Rui Hong Chemical Co., Ltd.s produce
Albumen stone flour, and the granularity of commercial protein stone flour is usually 200~1250 mesh, i.e. particle diameter is about 75~10 μm, however, as painting
Expect the powder of raw material, its particle diameter needs just make obtained coating fine and smooth below 2 μm, the product table coated with this coating
Face is smooth raised without particle, therefore, and present invention selection is ground processing to commercially available albumen stone flour, and d is made80Particle diameter is about 2 μ
M ultra-fine opal powder, using the ultra-fine opal powder as the smooth exquisiteness of composite granule made from nuclear material, is made coating
The quality of product is good.
The present invention uses wet grinding, to obtain ultra-fine opal powder, during wet grinding, due to albumen stone flour
It is easy to reunite, accordingly, it would be desirable to add dispersant in opal slurries, albumen stone flour is effectively disperseed, due to opal
Main component is Silicon dioxide, hydrate, therefore, it can add surfactant as dispersant, especially anionic surface work
Property agent, the preferably present invention surfactant such as Sodium Polyacrylate, triethanolamine and sodium pyrophosphate etc. that select, polyacrylic acid
Sodium.
Because the dispersion effect of dispersant and the viscosity of slurries are inversely proportional, i.e. the viscosity of slurries is smaller, dispersion effect
It is better, accordingly, it would be desirable to the viscosity of appropriate reduction opal slurries.
However, wet grinding has certain requirement to the viscosity of slurries, when slurries viscosity is too low, ball-milling medium it
Between the albumen stone flour that exists it is very few, cause ball-milling medium can not play a part of grinding to albumen stone flour, and then albumen stone flour is not
It can be ground as ultra-fine opal powder；Meanwhile, the viscosity of slurries can not be excessive, and otherwise ball-milling medium is in process of lapping
Retard motion, kinetic energy reduces, and the mechanical shock effect and shear action to albumen stone flour weaken, and are ground so as to can not fully play
The effect of mill, finally also leading to albumen stone flour can not be ground as ultra-fine opal powder.
The viscosity of opal slurries is influenceed by following two aspects factor：One is the solid content in slurries, and two be slurries
The concentration of middle dispersant, wherein,
The viscosity of slurries is directly proportional to the solid content of slurries, i.e. the solid content of slurries is bigger, and its viscosity is bigger；Slurry
The solid content of liquid is smaller, and its viscosity is smaller；
Because dispersant has certain viscosity, when dispersant concentration is excessive in slurries, the viscosity of slurries in itself
Also it can increase therewith.
Therefore, the solid content of present invention selection slurries is 50%~65%, preferably 55%~60%, such as 58%, disperse
The consumption of agent is the 0.1%~1.5%, preferably 0.5%~1.2% of opal dry powder weight, such as 1.0%, contain admittedly above-mentioned
Under amount and dispersant dosage, the viscosity of slurries is moderate, and albumen stone flour is neither reunited, and can rapidly be ground as d again80
Particle diameter is 2 μm of ultra-fine opal powder.
Step 2, by the ultra-fine opal slurry drying in step 1, ultra-fine opal powder is obtained, then use sodium silicate solution
Surface infiltration processing is carried out to it, then is dried at high temperature, modified superfine opal powder is made, adds water modified superfine egg
Albarium body is configured to modified superfine opal slurries.
It is noncrystal, therefore, its adsorption ability is weak, merely because the composition of opal is Silicon dioxide, hydrate
By opal and TiO2Surface coating is carried out by mechanical force and chemical, obtained product clad ratio is low, and follow-up ground
Easy coating easily comes off from the ultra-fine opal powder as nuclear material in journey, therefore, and present invention selection is to ultra-fine egg
Albarium body carries out surface modification.
The surface modifier that the present invention is selected is that both can be closely attached to opal by chemical bond or physical action
Surface, again can be with TiO2The material combined closely, simultaneously as the present invention is to prepare TiO by the method for mechanical force and chemical2/
Opal composite granule, i.e., to ultra-fine opal powder and TiO2The slurries of powder formation carry out mechanical agitation, pass through high-speed stirring
The impulsive force and shearing force of generation are mixed by TiO2Ultra-fine opal surface is compound to, therefore, the table of present invention selection good water solubility
Face modifying agent, preferably sodium metasilicate.
Sodium metasilicate, is commonly called as waterglass, is a kind of ore deposit binder, and it has the effect of micelle, sodium metasilicate in the dry state
The mol ratio of middle sodium oxide molybdena and silica is referred to as the modulus of sodium metasilicate.
The present inventor it has been investigated that, prepare TiO2During/opal composite granule, first to ultra-fine opal
Powder is surface-treated and is modified, then with TiO2Powder is configured to mixed serum, carries out mechanical force synthesis again afterwards, then TiO2
Powder is firmly combined with ultra-fine opal powder surface, is evenly coated, therefore, and the present inventor's selection has sodium metasilicate to ultra-fine first
Opal powder carries out surface modification.
The inventors discovered that, when sodium silicate solution concentration be more than 15.0wt% when, sodium silicate solution is excessively sticky, its with
Ultra-fine opal powder mixing is not uniform enough, causes the modification of ultra-fine opal powder uneven, or even caking；When sodium metasilicate is molten
When the concentration of liquid is less than 1.0%, sodium silicate solution concentration is too low, therefore, is needed when being modified to ultra-fine opal powder
A large amount of sodium silicate solutions are added, correspondingly, substantial amounts of solvent are introduced in ultra-fine opal powder, and these excessive solvents
Production cost, and the calcination time in increase subsequent high temperature calcination processing stage are not only increased, or even needs to increase elimination
The unnecessary step such as solvent, therefore, the concentration of present invention selection sodium silicate solution is 1.0wt%~15.0wt%, is preferably
3.0wt%~12.0wt%, more preferably 5.0wt%~10.0wt%, such as 8.0wt%.
In mixed serum, when the consumption of sodium metasilicate is more than the 6% of ultra-fine opal powder dry powder weight, slurries it is viscous
Denseness is excessive, in modifying process, and sodium metasilicate mixes uneven with ultra-fine opal powder, may cause to ultra-fine albumen stone flour
The modification of body is incomplete；When the consumption of sodium metasilicate is less than the 2% of ultra-fine opal powder dry powder weight, relative to ultra-fine albumen
Stone flour body, the consumption of sodium metasilicate is too small, and can not be powder-modified completely by ultra-fine opal, therefore, present invention selection sodium metasilicate
Consumption in terms of sodium metasilicate, be 2wt%~6wt% based on opal powder weight described in step (1), preferably 3wt%~
5wt%, such as 4wt%.
Meanwhile, the adhesivity of sodium metasilicate with its modulus increase first increases and then decreases, when the modulus of the sodium metasilicate of selection is small
When 2.0, the adhesivity of its sodium metasilicate is not enough, to TiO2The adhesive action played between ultra-fine opal powder is not enough；When
When the modulus of sodium metasilicate is more than 3.4, the adhesivity of sodium metasilicate can be reduced, and cause its adhesive action not enough, therefore, present invention selection
The modulus of sodium metasilicate is 2.0~3.4, preferably 2.4~3.0, such as 2.8.
Above-mentioned surface treated ultra-fine opal powder can quickly carry out surface modification under the high temperature conditions, but work as
When temperature is higher than 200 DEG C, sodium metasilicate and the key of ultra-fine opal powder surface formation are destroyed, and it is to ultra-fine opal powder
Modifying function disappears, and when temperature is less than 80 DEG C, Development of Modification is slow, therefore, and present invention selection modification temperature is 80 DEG C~200
DEG C, preferably 100 DEG C~160 DEG C, such as 140 DEG C.
Because present invention selection passes through mechanochemical method by TiO2Ultra-fine opal powder surface is coated on, is specially existed
Speed lapping stirring is carried out in liquid medium, the shearing force produced is stirred by speed lapping and is coated, therefore, by above-mentioned warp
Cross the modified ultra-fine opal powder in surface and be prepared as slurries, so as to TiO2Slurries are sufficiently mixed uniformly.
To make TiO prepared by subsequent step2- opal powder mixed serum has suitable solid content, quickly to fill
The formation TiO divided2/ opal composite granule, this step select the solid contents of modified opal powder slurries for 50%~
65%, preferably 55%~60%, such as 58%.
Step 3, by TiO2Powder is mixed with Sodium Polyacrylate or its solution, is stirred, is added water and TiO is made2Slurries.
Due to this it is bright in, TiO2Powder be used as opal powder Surface coating material, the present inventor it has been investigated that,
When the particle diameter of covering material is 1/10 or so of nuclear material particle diameter, it is evenly coated, and clad ratio is high, and it is used as the super of nuclear material
The d of small protein stone flour body80Particle diameter is 2 μm, therefore, present invention selection TiO2The particle diameter of powder is about 0.2 μm.
And the present invention is to TiO used2Powder source is not specially limited, and can be homemade TiO2Powder, or city
Any available TiO of mid-sales2The rutile type titanium white of powder, such as Jinan Yuxing Chemical Co., Ltd production
R818。
Due to TiO2The particle diameter of powder is 0.2 μm or so, and it easily reunites when preparing slurries, accordingly, it would be desirable to
Dispersant is added in slurries, the dispersant can be used identical with step 2, can also be with dispersant used in step 2
Difference, selected from Sodium Polyacrylate, triethanolamine and sodium pyrophosphate etc., preferably Sodium Polyacrylate.
Based on the same cause with the foregoing addition dispersant dosage in opal slurries, according to TiO2The viscosity of slurries
And dispersant is to TiO2The dispersion effect of powder, the consumption of present invention selection dispersant is TiO2The 0.3wt% of powder dry powder weight
~0.8wt%, preferably 0.4wt%~0.6wt%, such as 0.5wt%.
To make TiO2Slurries after being mixed with obtained modified superfine opal powder slurries in step 2 there is suitable consolidating to contain
Amount, present invention selection TiO2The solid content of slurries is 45%~55%, preferably 48%~52%, such as 50%.
Step 4, by obtained modified superfine opal powder slurries in step 2 and obtained TiO in step 32Slurries are mixed
Close, and solid content in mixed serum is ground to d98Particle diameter is 2 μm, and TiO is made2/ opal composite granule slurries.
The present inventor it has been investigated that, when using ultra-fine opal powder as nuclear material, with TiO2When powder is covering material,
20~40wt% of cladding is only needed on nuclear material (with TiO2The gross weight meter of/opal composite granule) covering material
Reach and commercially available titanium dioxide identical action effect, therefore, present invention selection modified superfine opal powder slurries and TiO2Slurry
Liquid is according to TiO2The ratio of powder dry powder weight and modified superfine opal powder dry powder weight is TiO2Powder dry powder weight:Change
Ultra-fine opal powder dry powder weight=1 of property:(4~1.5), preferably 1:(3~2), such as 1:2.5 are mixed.
However, using other materials as nuclear material, it is necessary to TiO2Consumption be 40~60wt%, you can to reduce cladding material
Expect TiO220~40wt% of powder consumption, so as to greatly save cost.
The present invention carries out mechanical force grinding by wet grinding method to above-mentioned mixed serum, so that the TiO in slurries2It is small
Particle is more abundant and is equably coated on modified superfine opal powder surface, and makes the d of composite particles to be formed98Particle diameter
For 2 μm.
Step 5, by obtained TiO in step 42/ opal composite granule slurry dilution, filtering, then filter cake is washed
Wash, finally break up filtration cakes torrefaction.
Dispersant and sodium metasilicate are remained in ultrathin composite powder slurries made from step 4, and above-mentioned two classes material is equal
It is water-soluble, it therefore, it can remove above-mentioned two classes material by washing filtering, moreover, filtrate can be recycled in abovementioned steps
Recycle.
The filter cake filtered as TiO2/ opal composite granule, breaks up as finished product, the TiO after drying2/ opal is combined
The d of powder98Particle diameter is 2 μm.
Its scanning electron microscope (SEM) photograph is as shown in Figure 1.
Embodiment
The commercially available information of the present embodiment agents useful for same is as follows：
Opal powder：Shanghai Rui Hong Chemical Co., Ltd.s；
TiO2：The rutile type titanium white R818 of Jinan Yuxing Chemical Co., Ltd's production；
Sodium Polyacrylate：The sour sodium of food-grade polypropylene of Henan Jin Run food additives Co., Ltd production；
Sodium metasilicate：The sodium metasilicate that the modulus of Yongqing County Ju Li get Chemical Co., Ltd.s production is 2.6~2.9.
Embodiment 1
(1) sodium polyacrylate solution (containing Sodium Polyacrylate 1.0g) is added into 100g opals powder (1250 mesh), then
Water is added, the slurries that solid content is 60% are made, opal powder is crushed to d80Particle diameter is 2 μm of ultra-fine opal slurry；
(2) by the ultra-fine opal slurry drying in step (1), ultra-fine opal powder is obtained, then be with concentration
10.0%, modulus is surface-treated for 2.8 sodium silicate solution (containing sodium metasilicate 4g) to it, then the dry modification at 180 DEG C,
Modified superfine opal powder is made, then modified superfine opal powder is configured to the modified superfine albumen that solid content is 60%
Stone slurries；
(3) by 30g TiO2Powder is mixed with sodium polyacrylate solution (containing Sodium Polyacrylate 0.5g), is stirred, is added water
The TiO that solid content is 50% is made2Slurries；
(4) by obtained modified superfine opal slurries in step (2) and obtained TiO in step (3)2Slurries are mixed,
And solid content in mixed serum is ground to d98Particle diameter is 2 μm, and TiO is made2/ opal composite granule slurries；
(5) by obtained TiO in step (4)2/ opal composite granule slurries are diluted with water, filtering, then filter cake is carried out
Washing, finally breaks up filtration cakes torrefaction, and TiO is made2/ opal composite granule.
Obtained TiO2Its whiteness of/opal composite granule is 93.6, and covering power is 15.6g/m2, ESEM such as Fig. 1 institutes
Show, as seen from Figure 1, after treatment, titanium dioxide is evengranular to be coated on ultra-fine opal particle surface, forms TiO2/ egg
White stone composite granule.
Embodiment 2
(1) sodium polyacrylate solution (containing Sodium Polyacrylate 1.0g) is added into 100g opals powder (500 mesh), then is added
Enter water, the slurries that solid content is 65% are made, opal powder is crushed to d80Particle diameter is 2 μm of ultra-fine opal slurry；
(2) by the ultra-fine opal slurry drying in step (1), ultra-fine opal powder is obtained, then be with concentration
15.0%, modulus is surface-treated for 3.4 sodium silicate solution (containing sodium metasilicate 6g) to it, then the dry modification at 200 DEG C,
Modified superfine opal powder is made, then modified superfine opal powder is configured to the modified superfine albumen that solid content is 58%
Stone slurries；
(3) by 33g TiO2Powder is mixed with sodium polyacrylate solution (containing Sodium Polyacrylate 0.3g), is stirred, is added water
The TiO that solid content is 45% is made2Slurries；
(4) by obtained modified superfine opal slurries in step (2) and obtained TiO in step (3)2Slurries are mixed,
And solid content in mixed serum is ground to d98Particle diameter is 2 μm, and TiO is made2/ opal composite granule slurries；
(5) by obtained TiO in step (4)2/ opal composite granule slurries are diluted with water, filtering, then filter cake is carried out
Washing, finally breaks up filtration cakes torrefaction, and TiO is made2/ opal composite granule.
Obtained TiO2/ opal composite granule whiteness is 94.2, and covering power is 14.3g/m2, scanning electron microscope (SEM) photograph such as Fig. 2 institutes
Show, from Figure 2 it can be seen that utilizing TiO made from the present embodiment2/ opal composite granule, titanium dioxide is uniformly coated on ultra-fine egg
The surface of albarium body particle.
Embodiment 3
(1) sodium polyacrylate solution (containing Sodium Polyacrylate 0.1g) is added into 100g opals powder (200 mesh), then is added
Enter water, the slurries that solid content is 50% are made, opal powder is crushed to d80Particle diameter is 2 μm of ultra-fine opal slurry；
(2) by the ultra-fine opal slurry drying in step (1), ultra-fine opal powder is obtained, then be with concentration
1.0%, modulus is surface-treated for 2.0 sodium silicate solution (containing sodium metasilicate 2g) to it, then the dry modification at 180 DEG C,
Modified superfine opal powder is made, then modified superfine opal powder is configured to the modified superfine albumen that solid content is 50%
Stone slurries；
(3) by 25g TiO2Powder is mixed with sodium polyacrylate solution (containing Sodium Polyacrylate 0.8g), is stirred, is added water
The TiO that solid content is 50% is made2Slurries；
(4) by obtained modified superfine opal slurries in step (2) and obtained TiO in step (3)2Slurries are mixed,
And solid content in mixed serum is ground to d98Particle diameter is 2 μm, and TiO is made2/ opal composite granule slurries；
(5) by obtained TiO in step (4)2/ opal composite granule slurries are diluted with water, filtering, then filter cake is carried out
Washing, finally breaks up filtration cakes torrefaction, and TiO is made2/ opal composite granule.
Obtained TiO2/ opal composite granule whiteness is 93.1, and covering power is 14.4g/m2, scanning electron microscope (SEM) photograph such as Fig. 3 institutes
Show, as seen from Figure 3, ultra-fine opal powder is uniformly coated on using titanium dioxide in composite granule made from the present embodiment
The surface of grain.
Embodiment 4
(1) sodium polyacrylate solution (containing Sodium Polyacrylate 1.0g) is added into 100g opals powder (1250 mesh), then
Water is added, the slurries that solid content is 58% are made, opal powder is crushed to d80Particle diameter is 2 μm of ultra-fine opal slurry；
(2) by the ultra-fine opal slurry drying in step (1), ultra-fine opal powder is obtained, then be with concentration
8.0%, modulus is surface-treated for 2.8 sodium silicate solution (containing sodium metasilicate 4g) to it, then the dry modification at 180 DEG C,
Modified superfine opal powder is made, then modified superfine opal powder is configured to the modified superfine albumen that solid content is 50%
Stone slurries；
(3) by 25g TiO2Powder is mixed with sodium polyacrylate solution (containing Sodium Polyacrylate 0.5g), is stirred, is added water
The TiO that solid content is 58% is made2Slurries；
(4) by obtained modified superfine opal slurries in step (2) and obtained TiO in step (3)2Slurries are mixed,
And solid content in mixed serum is ground to d98Particle diameter is 2 μm, and TiO is made2/ opal composite granule slurries；
(5) by obtained TiO in step (4)2/ opal composite granule slurries are diluted with water, filtering, then filter cake is carried out
Washing, finally breaks up filtration cakes torrefaction, and TiO is made2/ opal composite granule.
Obtained TiO2/ opal composite granule whiteness is 94.8, and covering power is 14.3g/m2, scanning electron microscope (SEM) photograph such as Fig. 4 institutes
Show, from fig. 4, it can be seen that being uniformly coated on ultra-fine opal powder using titanium dioxide in composite granule made from the present embodiment
The surface of grain.
Comparative example
Comparative example 1
This comparative example is same as Example 1, differs only in no step (2), the whiteness of obtained product is 91.8, is covered
Power is 18.3g/m2, scanning electron microscope (SEM) photograph as shown in figure 5, as seen from Figure 5, titanium white powder particles are uncoated in opal particle surface,
But with ultra-fine opal particle dispersion mixing, form common mixture.
The present invention is described in detail above in association with embodiment and exemplary example, but these explanations are simultaneously
It is not considered as limiting the invention.It will be appreciated by those skilled in the art that without departing from the spirit and scope of the invention,
A variety of equivalencings, modification can be carried out to technical solution of the present invention and embodiments thereof or is improved, these each fall within the present invention
In the range of.Protection scope of the present invention is determined by the appended claims.
Claims (3)
1. one kind prepares TiO2The method of/opal composite granule, it is characterised in that this method comprises the following steps：
（1）Sodium Polyacrylate or its solution are added into opal powder, water is added, slurries is made, by opal powder powder
It is broken to d80Particle diameter is 2 μm of ultra-fine opal slurry,
The addition of the Sodium Polyacrylate or its solution, based on opal powder weight, is in terms of Sodium Polyacrylate weight
0.5%~1.2%；
The solid content that slurries are made is 55% ~ 60%, wherein, the solid content refers to solid content weight and slurries gross weight in slurries
Ratio；
（2）By step（1）In ultra-fine opal slurry drying, obtain ultra-fine opal powder, then with sodium silicate solution to it
Surface infiltration processing is carried out, then is dried at 80 ~ 200 DEG C, modified superfine opal powder is made, adds water modified superfine egg
Albarium body is configured to modified superfine opal slurries,
The concentration of the sodium silicate solution is 3.0wt% ~ 12.0wt%；
The addition of the sodium silicate solution is in terms of sodium metasilicate, based on step（1）Described in opal powder weight, be 3wt% ~
5wt%；
The solid content of the modified superfine opal slurries is 55% ~ 60%, wherein, the solid content refers to solid content weight in slurries
The ratio of amount and slurries gross weight；
（3）By TiO2Powder is mixed with Sodium Polyacrylate or its solution, is stirred, is added water and TiO is made2Slurries,
The addition of the Sodium Polyacrylate or its solution is in terms of Sodium Polyacrylate, based on opal powder weight, be 0.4wt% ~
0.6wt%；
The obtained TiO2The solid content of slurries is 48% ~ 52%, wherein, the solid content refers to solid content weight and slurry in slurries
The ratio of liquid gross weight；
（4）By step（2）In obtained modified superfine opal slurries and step（3）In obtained TiO2Slurries are mixed, and will be mixed
Close solid content in slurries and be ground to d98Particle diameter is 2 μm, and TiO is made2/ opal composite granule slurries,
The modified superfine opal slurries and TiO2Slurries are according to modified superfine opal powder dry powder weight and TiO2Powder is done
The ratio of powder weight is TiO2Powder dry powder weight:Modified superfine opal powder dry powder weight=1:（3~2）；
（5）By step（4）In obtained TiO2/ opal composite granule slurry dilution, filtering obtains filter cake, then filter cake is carried out
Washing, finally breaks up filtration cakes torrefaction.
2. according to the method described in claim 1, it is characterised in that in step（2）In, the concentration of the sodium silicate solution is
5.0wt% ~ 10.0wt%, modulus is 2.4 ~ 3.0.
3. according to the method described in claim 1, it is characterised in that in step（2）In, by step（1）In ultra-fine opal
Slurry drying, obtains ultra-fine opal powder, then surface infiltration processing is carried out with sodium silicate solution to it, then in temperature is 100
DEG C ~ 160 DEG C at dry.
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| CN102993785A (en) * | 2012-11-13 | 2013-03-27 | 王丕轩 | Preparation method for TiO2/opal composite powder material |
| CN103305030A (en) * | 2012-03-07 | 2013-09-18 | 中国地质大学（北京） | Preparation method of iron oxide red/diatomite composite powder pigment |
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| CN103305030A (en) * | 2012-03-07 | 2013-09-18 | 中国地质大学（北京） | Preparation method of iron oxide red/diatomite composite powder pigment |
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