CN100580030C - Process for preparing core-shell structure TiO2/Ca2CO3 composite white pigment - Google Patents
Process for preparing core-shell structure TiO2/Ca2CO3 composite white pigment Download PDFInfo
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- CN100580030C CN100580030C CN200610117441A CN200610117441A CN100580030C CN 100580030 C CN100580030 C CN 100580030C CN 200610117441 A CN200610117441 A CN 200610117441A CN 200610117441 A CN200610117441 A CN 200610117441A CN 100580030 C CN100580030 C CN 100580030C
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- calcium hydroxide
- carbonate
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Abstract
The present invention discloses preparation process of white composite TiO2/CaCO3 pigment in core-shell structure. The preparation process includes adding titania into calcium hydroxide suspension, adding calcium ion concentration regulator, and adding carbonate solution to produce calcium carbonate particle deposited on the surface of titanium white particle to form the shell and to produce the composite material in core-shell structure inside the suspension. The present invention has simple preparation process, stable product performance, and compact CaCO3 shell structure to avoid agglomeration of titania particle. The prepared white pigment has low cost and may be used in paper filler and paint to replace available titanium white powder for raised product quality.
Description
Technical field
The present invention relates to TiO
2/ CaCO
3The preparation method of composite white pigment specifically, relates to the TiO with nucleocapsid structure of paper grade (stock)
2/ CaCO
3The preparation method of composite white pigment.
Background technology
Titanium dioxide (TiO
2), be commonly called as titanium dioxide, be the different white pigment of best performance up to now.It has stable physics, chemical property, and good opacifying power, tinting strength, photo and thermal stability are widely used in fields such as coating, plastics, papermaking, chemical fibre, printing ink, rubber.The main crystal habit of titanium dioxide has two kinds, i.e. anatase titanium dioxide and rutile-type, and the latter has better opacifying power and weathering resistance.Along with the development of world economy and the progress of human science and technology, the Application Areas of titanium dioxide is more and more wider, and the market demand of titanium dioxide also grows with each passing day.And on the other hand, since the shortage day by day of world's high-quality titanium resource, the product processes complexity, technical difficulty is big, and environmental protection requirement is more and more stricter, and these all cause the titanium white production cost to increase, and price raises up.Therefore, seek effective substitute (abbreviation composite titanium dioxide) of titanium dioxide, becoming reduces cost overcomes the important channel of shortage of resources.
The technology of disclosed preparation composite titanium dioxide mainly contains three class modes at present:
1. at inorganic mineral material surface cladding titanium dioxide.For example CN 1206727A discloses a kind of nano-TiO
2The preparation method of/ore powder composite titanium dioxide, this is invented with TiOSO
4, Ti (SO
4)
2, TiCl
4Deng being raw material, by hydrolysis reaction at ore powder coated with uniform one deck nano level superfine TiO
2Make nano combined titanium white.But owing to need high-temperature calcination to handle, particle takes place to reunite and grow up easily, influences its pigment performance.And for example CN 1724595A discloses a kind of white mineral powder-TiO
2Composite white pigment and preparation method thereof, this invention use lime carbonate, kaolin, calcined kaolin etc. to be bag nuclear matrix, crystal TiO
2Be the coating thing, realize TiO by wet grinding
2At the reaction coating and the modifying and decorating of bag nuclear matrix surface, Zhi Bei white mineral powder-TiO thus
2Composite white pigment has the character of pigmentary titanium dioxide.But this method coats lack of homogeneity to the equipment requirements height, and cost is higher.CN 1444543A discloses a kind of titanium dioxide-calcium carbonate composite particles, it is by under agitation importing carbon dioxide and AIR MIXTURES in calcium hydroxide slurry, carry out carbonation reaction, and in carbonation, add the TiO 2 particles of 0.1～0.5 micron of median size, make it directly load on the synthetic calcium carbonate surface and form composite particles.Yet because its particle combination is mainly by physical adsorption (as electrostatic attraction), so titanium dioxide easily breaks away from calcium carbonate particles and weakens its performance in application.
2. at titanium dioxide coated with carbon acid calcium.For example CN 1724595A discloses pigment particles of a kind of coated with precipitated calcium carbonate and preparation method thereof.This invention is pigment particles, and as titanium dioxide, and precipitated chalk mixes at aqueous phase time together in pH6～11, and the precipitated lime carbonate powder of pigment particles is applied, and the brightness of this product is good, and preparation cost reduces.Yet pigment particles and lime carbonate are to combine by van der waals forces, this kind bonding force a little less than, easily take place to separate in post-processed or in using and cause the weakening of performance.
3. lime carbonate-titanium dioxide mixed type pigment.Promptly make lime carbonate and the mutual uniform mixing of titanium dioxide by the whole bag of tricks, because the titanium dioxide particle is separated by lime carbonate, therefore can avoid reuniting between the titanium dioxide particle, improve the application performance of titanium dioxide, as be applied in papermaking filler, can improve retention and paper opaqueness etc.For example US 3,832,206 disclose a kind of preparation method of composite pigment, with a certain amount of titanium dioxide and concentration is the calcium hydroxide slurry of 100～225g/L or a kind of mixing that concentration is 100～250g/L sodium carbonate solution, in 30～60 minutes, another kind of solution is mixed with above-mentioned mixing suspension then, the gained composite mortar after filtration, the washing after drying promptly get product.Yet this method is because reaction raw materials concentration is higher, and the reaction times is too short, lime carbonate tends to the homogeneous nucleation growth, be difficult to coat at the titanium dioxide granule surface filming, therefore described as this patent, the gained composite pigment only forms certain bonding through electron microscopic observation titanium dioxide and calcium carbonate granule between contact surface, be still a kind of mixture basically.Therefore in order to obtain the performance similar with titanium dioxide, as opacifying power and opaqueness, the content of titanium dioxide need account for 50～80% of composite pigment total mass in the composite pigment of this method preparation.The effect that it reduces titanium dioxide consumption, reduce cost is limited.
Summary of the invention
The objective of the invention is provides a kind of TiO with nucleocapsid structure in order to overcome the defective of prior art
2/ CaCO
3The preparation method of composite white pigment.
Technical conceive of the present invention is such:
The present invention's imagination makes calcium hydroxide and soluble carbon hydrochlorate that following reaction take place in liquid phase:
Ca
2++CO
3 2-→CaCO
3↓
The CaCO that generates
3In the growth of titanium dioxide particle surface heterogeneous nucleation, by control CaCO
3Formation speed, with the coating that obtains even compact and do not produce precipitation from homogeneous solution (PFHS).
Calcium hydroxide is a kind of insoluble alkali, and it is slightly soluble in water, has following ionization equilibrium in water:
Its solubility product constant K at normal temperatures
Sp=5.5 * 10
-6Therefore, select calcium hydroxide, can make the Ca that participates in reaction as reactant
2+Ionic concn is lower, slowly releases Ca in the reaction process
2+Ion, CaCO in the feasible reaction
3Formation speed slower, help heterogeneous nucleation growth.
The inventor further finds, adds the calcium ion concn conditioning agent before reaction, with Ca
2+Ionic concn is adjusted to 1 * 10
-5～1 * 10
-2Mol, i.e. OH
-Ionic concn is 0.02～0.74 mol, can make the lime carbonate of generation be coated on TiO 2 particles surface formation nucleocapsid structure fully, and can not form independent calcium carbonate granule.
Reaction times is very big to forming which kind of matrix material influence.Reaction times is shorter, can produce a large amount of calcium carbonate granules in moment, cause lime carbonate excessive concentration in the system, and be more prone to homogeneous nucleation, finally can only form lime carbonate-titanium dioxide blends or only can form the mixture of surface adsorption.The inventor finds that the reaction times was controlled at 3～8 hours, can effectively control the formation speed of lime carbonate, helped heterogeneous nucleation, thereby obtained the titanium dioxide-calcium carbonate matrix material of nucleocapsid structure.
The contriver finishes the present invention based on above-mentioned discovery.
Method of the present invention comprises the steps:
Titanium dioxide is added calcium hydroxide suspension, add the calcium ion concn conditioning agent then, the system calcium ion concn is controlled at 1 * 10
-2～1 * 10
-5Mol added carbonate solution in calcium hydroxide-titanium dioxide mixing suspension in 3～8 hours, made the calcium carbonate particles of generation be deposited on the titanium dioxide particle surface and formed shell, obtained having the suspension of the matrix material of nucleocapsid structure;
Gained suspension after filtration, the washing after, can drying make the powder form, also drying is not directly made slurry form, satisfies different needs.Filtration, washing and drying all can adopt ordinary method;
The concentration of calcium hydroxide suspension is 10～125g/L, preferred 10～50g/L;
The crystal formation of said titanium dioxide can be an anatase titanium dioxide, can be rutile-type, also can be both mixtures by any ratio;
Said calcium ion concn conditioning agent is selected from one or more of sodium hydroxide, potassium hydroxide or ammoniacal liquor;
Carbonate is one or more of volatile salt, bicarbonate of ammonia, yellow soda ash, sodium bicarbonate, salt of wormwood or saleratus, and the concentration of soluble carbon acid salt solution is preferably 50～100g/L;
Carbonate: calcium hydroxide=1: 0.95～1.05, mol ratio;
It is 25%～85% of titanium dioxide and calcium hydroxide gross weight that titanium dioxide adds weight.Preparation method's process simple controllable disclosed in this invention, product performance are stable, compact calcium carbonate, evenly and securely be deposited on titanium dioxide granule surface and form shell, well avoid the reunion of titanium dioxide granule, show the natural characteristics of titanium dioxide to greatest extent, the gained composite white pigment can reduce cost when keeping the titanium dioxide performance significantly.This composite white pigment replaces titanium dioxide application and papermaking filler or coating, can improve paper whiteness and opaqueness.
Description of drawings
Fig. 1 is the transmission electron microscope photo of embodiment 1.
Embodiment
Embodiment 1
Preparation calcium hydroxide content is 125g/L suspension 0.474L in reactor, adds the 20g anatase titanium dioxide, stirs; Add 0.51g potassium hydroxide, the system calcium ion concn is controlled at about 1.5 * 10
-2Mol; Compound concentration is 250g/L sodium carbonate solution 0.34L; In 3 hours, sal volatile is added in calcium hydroxide-titanium dioxide mixing suspension, make slow generation calcium carbonate particles and be deposited on the titanium dioxide particle surface to form shell, obtain having the matrix material of nucleocapsid structure; Gained suspension after filtration, the washing after, 110 ℃ of dryings are made the composite white pigment dry powder that contains 20% titanium dioxide.The products therefrom transmission electron microscope observing, particle is nucleocapsid structure.Transmission electron microscope photo is seen Fig. 1.
Paper adds to tamp to be tested: in needle slurry (45 ° of SR): the ratio making beating of broad-leaved slurry (25 ° of SR)=40: 60, pulp material 120g/m is copied in design
2After load weighted paper pulp stirred 1 minute, add titanium dioxide or composite white pigment, it is 30% (in oven dry stock) that filler adds the amount of filling out, and stirs 1 minute, adds the polyacrylamide of 500PPM again, take off after stirring half a minute, on the square handshcet former, copy sheet, under the pressure of 0.3MPa press polish once, equilibrium water content under 105 ℃ of baking oven slaking 20min normal temperature.
Quantitatively measuring of pattern according to GB/T 451.2-2002, whiteness is measured according to GB/T7974-2002, and opaqueness is measured according to GB/T 1543-2005, and tensile strength is measured according to GB/T 453-2002, and ash content is measured according to GB/T 742-2003.Every physical index of paper sees Table 1.
Table 1. pattern physical index relatively
Embodiment 2
Preparation calcium hydroxide content is 10g/L suspension 1L in reactor, adds the 108g anatase titanium dioxide, stirs; Add 29.6g sodium hydroxide, the system calcium ion concn is controlled at about 1 * 10
-5Mol; Compound concentration is 50g/L sal volatile 0.26L; In 8 hours, sal volatile is added in calcium hydroxide-titanium dioxide mixing suspension, make slow generation calcium carbonate particles and be deposited on the titanium dioxide particle surface to form shell, obtain having the matrix material of nucleocapsid structure; Gained suspension after filtration, the washing after, 110 ℃ of dryings are made the composite white pigment dry powder that contains 80% titanium dioxide.The products therefrom transmission electron microscope observing, particle is nucleocapsid structure.
Adopt and to carry out paper with embodiment 1 identical method and add to tamp and test, the result is as shown in table 2:
Table 2. pattern physical index relatively
Embodiment 3
Preparation calcium hydroxide content is 49.33g/L suspension 0.9L in reactor, adds the 40g rutile titanium dioxide, stirs; Add 3.78g sodium hydroxide, the system calcium ion concn is controlled at about 5 * 10
-4Mol; Compound concentration is 100.8g/L sodium hydrogen carbonate solution 0.5L; In 5 hours, sodium hydrogen carbonate solution is added in calcium hydroxide-titanium dioxide mixing suspension, make slow generation calcium carbonate particles and be deposited on the titanium dioxide particle surface to form shell, obtain having the matrix material of nucleocapsid structure; Gained suspension after filtration, after the washing, adding water, to make solid content be 45% slurry.The products therefrom transmission electron microscope observing, particle is nucleocapsid structure.
Adopt and to carry out paper with embodiment 1 identical method and add to tamp and test, the result is as shown in table 3:
Table 3. pattern physical index relatively
Claims (7)
1. nucleocapsid structure TiO
2/ CaCO
3The preparation method of composite white pigment is characterized in that, comprises the steps: titanium dioxide is added calcium hydroxide suspension, adds the calcium ion concn conditioning agent then, and the system calcium ion concn is controlled at 1 * 10
-5～1 * 10
-2Mol added carbonate solution in calcium hydroxide-titanium dioxide mixing suspension in 3～8 hours, made the calcium carbonate particles of generation be deposited on the titanium dioxide particle surface and formed shell, obtained having the suspension of the matrix material of nucleocapsid structure;
Said calcium ion concn conditioning agent is selected from more than one of sodium hydroxide, potassium hydroxide or ammoniacal liquor.
2. method according to claim 1 is characterized in that, gained suspension after filtration, the washing after, drying is made the powder form, or directly makes slurry form.
3. method according to claim 1 is characterized in that, the concentration of calcium hydroxide suspension is 10～125g/L.
4. method according to claim 3 is characterized in that, the concentration of calcium hydroxide suspension is 10～50g/L.
5. method according to claim 1 is characterized in that, the crystal formation of said titanium dioxide is a kind of in anatase titanium dioxide or the rutile-type or both mixtures by any ratio.
6. method according to claim 1, it is characterized in that, carbonate is one or more of volatile salt, bicarbonate of ammonia, yellow soda ash, sodium bicarbonate, salt of wormwood or saleratus, the concentration of soluble carbon acid salt solution is 50～100g/L, carbonate: calcium hydroxide=1: 0.95～1.05, mol ratio.
7. method according to claim 1 is characterized in that, it is 25%～85% of titanium dioxide and calcium hydroxide gross weight that titanium dioxide adds weight.
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101079363B (en) * | 2007-06-14 | 2010-06-09 | 中南大学 | Nucleus-shell cathode emission material for fluorescent tube and its making method |
| CN103194098B (en) * | 2013-04-07 | 2015-04-08 | 攀枝花学院 | Preparation method of composite titanium dioxide |
| CN104893364A (en) * | 2015-06-03 | 2015-09-09 | 安徽省铜陵县牛山矿业有限责任公司 | Production technique and production line of mineral/TiO2 composite granular material |
| CN105093829B (en) * | 2015-07-07 | 2019-06-28 | 合肥鑫晟光电科技有限公司 | A kind of composite white pigment, the photoresist containing the pigment and its application |
| CN107190570A (en) * | 2017-06-29 | 2017-09-22 | 滁州卷烟材料厂 | A kind of preparation method of cork paper body paper |
| CN109251557B (en) * | 2018-07-12 | 2021-04-02 | 广西华纳新材料科技有限公司 | Preparation method of core-shell structure nano precipitated calcium carbonate |
| CN112876878A (en) * | 2021-01-26 | 2021-06-01 | 江西势通钙业有限公司 | Ultrahigh-whiteness pigment-grade core-shell structure type nano calcium carbonate and preparation method thereof |
| CN115490261B (en) * | 2022-10-20 | 2023-11-24 | 福建乐钛科技有限公司 | Titanium dioxide for antibacterial and mildew-proof chemical fiber and preparation method thereof |
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Effective date of registration: 20171102 Address after: Xinglongzhuang Town Industrial Park, Jining District of Yanzhou City, Shandong province 272100 Patentee after: Jining Ming Sheng new material Co., Ltd. Address before: 200235, room 100, 1002 Qinzhou Road, Shanghai, Xuhui District Patentee before: Shanghai Dongsheng new material Co., Ltd. |
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