CN100484880C - Low-temperature crystallized nano titanium dioxide powder and synthesis method of sol - Google Patents
Low-temperature crystallized nano titanium dioxide powder and synthesis method of sol Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 19
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000001308 synthesis method Methods 0.000 title abstract 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 30
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims abstract description 24
- 239000010936 titanium Substances 0.000 claims abstract description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 36
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 28
- 238000003916 acid precipitation Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 230000007062 hydrolysis Effects 0.000 claims description 11
- 238000006460 hydrolysis reaction Methods 0.000 claims description 11
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 9
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 6
- 239000011707 mineral Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 238000010790 dilution Methods 0.000 claims description 5
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- 239000006185 dispersion Substances 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 238000010189 synthetic method Methods 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 238000001953 recrystallisation Methods 0.000 claims description 4
- 239000002893 slag Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000003809 water extraction Methods 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 241000237502 Ostreidae Species 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 230000000887 hydrating effect Effects 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 235000020636 oyster Nutrition 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 abstract description 13
- 239000002244 precipitate Substances 0.000 abstract description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 abstract description 4
- 239000007791 liquid phase Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000002159 nanocrystal Substances 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 239000011941 photocatalyst Substances 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 7
- 229960000907 methylthioninium chloride Drugs 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
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- -1 titanium organic compound Chemical class 0.000 description 4
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- 239000004033 plastic Substances 0.000 description 3
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 230000000968 intestinal effect Effects 0.000 description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000012463 white pigment Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical class [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- LFSBSHDDAGNCTM-UHFFFAOYSA-N cobalt(2+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Co+2] LFSBSHDDAGNCTM-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- PHGMGTWRSNXLDV-UHFFFAOYSA-N diethyl furan-2,5-dicarboxylate Chemical compound CCOC(=O)C1=CC=C(C(=O)OCC)O1 PHGMGTWRSNXLDV-UHFFFAOYSA-N 0.000 description 1
- DGXKDBWJDQHNCI-UHFFFAOYSA-N dioxido(oxo)titanium nickel(2+) Chemical compound [Ni++].[O-][Ti]([O-])=O DGXKDBWJDQHNCI-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- SOBXOQKKUVQETK-UHFFFAOYSA-H titanium(3+);trisulfate Chemical compound [Ti+3].[Ti+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O SOBXOQKKUVQETK-UHFFFAOYSA-H 0.000 description 1
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Abstract
The invention belongs to a preparation process of an inorganic metal oxide-titanium dioxide photocatalyst, and particularly relates to a synthesis method of low-temperature crystallized nano titanium dioxide powder and sol with high catalytic activity. The invention utilizes alkali to neutralize, dilute and hydrolyze or heat hydrolyzed titanium liquid to obtain normal titanic acid precipitate, and utilizes the treatment process of hydrogen peroxide to re-disperse the precipitate, thereby realizing the method for synthesizing the related system nanocrystal material by normal pressure and low temperature liquid phase. Not only greatly reduces the cost on raw materials, but also avoids using titanium tetrachloride with strong corrosivity and reduces the requirement on equipment.
Description
Technical field
The invention belongs to the preparation technology of inorganic, metal oxide-titanium dioxide optical catalyst, especially relate to the low temperature crystallized nano titanium dioxide powder that possesses high catalytic activity and the synthetic method of colloidal sol.
Background technology
Titanium dioxide is important Inorganic Chemicals, at coating, and printing ink, papermaking, plastics, rubber is used as white pigment in the industry such as synthon; Simultaneously, at pottery, welding electrode, electronics, metallurgy etc. are industrial also important application.Synthesizing of powder titanium dioxide generally has sulfuric acid process and two kinds of explained hereafter of chlorination process: traditional sulfuric acid process industrial production titanium dioxide long flow path, and three waste discharge is many, and the product cut size that obtains is big and inhomogeneous, and is wayward; And chlorination process is to the ingredient requirement height, and equipment corrosion is serious, the preparation condition harshness.
TiO 2 sol is with a wide range of applications as the uniform and stable dispersion system of nano titanium oxide, can be used for the synthetic or automatically cleaning high grade paint of photocatalytic film coating etc.At present, prepare the method that TiO 2 sol generally adopts titanium organic compound control hydrolysis or Ti-inorganic salt hydrolysis.Utilize the method for titanium organic compound control hydrolysis to prepare titanium dioxide nano sol,, improved cost greatly because the titanium organic compound costs an arm and a leg; Simultaneously, owing to adopt pure water mixed hydrolysis, the product that obtains is an organic solution, limits its application on hydrophilic base.And adopt the Ti-inorganic salt hydrolysis, and need additional steps such as high-temperature water thermal crystallisation, not only need specific installation and device, increased cost, also the limit production scale.
Patent as the compound anion method for preparing rutile type titanium dioxide of number of patent application 91101522.1, it discloses and has utilized sulfuric acid to decompose ilmenite to obtain titanium sulfate solution and add composite anion and prepare rutile titanium dioxide, but it needs follow-up 800～900 ℃ high temperature crystallization process, this has not only increased the apparatus and process difficulty and has raised the cost, and also can increase particle diameter owing to high temperature sintering causes powder reuniting simultaneously.
Hiroaki Katsuki[Journal of the Ceramic Society of Japan 106[3] 344～347 1998] reported that the titanic Acid precipitation that utilizes hydroperoxide dissolution to be obtained by titanium tetrachloride hydrolysis prepares the method for TiO 2 sol.Because it adopts the corrodibility titanium tetrachloride is presoma, to the equipment requirements height, thereby industrial production cost is too high.
Summary of the invention
The objective of the invention is to prepare on the traditional method basis of anatase titanium dioxide in sulfuric acid process, providing is the synthetic method of the low temperature crystallized nano titanium dioxide powder and the colloidal sol of raw material with the ilmenite; Realize normal pressure, low temperature liquid phase synthesis of nano titanium dioxide.
The present invention has realized the method that normal pressure, low temperature liquid phase are synthesized the related system nano crystal material by the further investigation to titanium dioxide nucleation and growth process.Not only on starting material, greatly reduce cost, and avoid the titanium tetrachloride that uses corrodibility strong, reduced requirement equipment.
Key point of the present invention is to utilize alkali neutralization, dilution hydrolysis or heating hydrolysis titanium liquid to obtain the titanic Acid precipitation and utilizes hydrogen peroxide that precipitation is disperseed this treatment process again.
The synthetic method of low temperature crystallized nano titanium dioxide powder of the present invention and colloidal sol may further comprise the steps:
(1) acidolysis
With concentration is 70～98% sulfuric acid heating for dissolving ilmenite or metatitanic acid compounds, and the solid precipitation thing that obtains obtains titanium liquid with water extraction, wherein ilmenite or metatitanic acid compounds: the vitriolic mass ratio is 1:2;
Or utilize titanium sulfate, titanous sulfate or titanyl sulfate hydrolysis to generate titanium liquid;
(2) titanium liquid purifies
The titanium liquid of step (1) is removed by filter insoluble slag, and frozen recrystallization removes by filter impurity, obtains titaniferous precursor solution;
(3) hydrating solution obtains the titanic Acid precipitation
The pH value that adds the titaniferous precursor solution of alkali neutralization procedure (2) is about 5～11, obtains the titanic Acid precipitation;
Or the titaniferous precursor solution of dilution hydrolysing step (2), obtain the titanic Acid precipitation;
Or the titaniferous precursor solution of heating hydrolysis step (2), obtain the titanic Acid precipitation;
Describedly add alkali neutralization and can adopt alkali electroless reagent neutralizations such as yellow soda ash, sodium bicarbonate, salt of wormwood, saleratus, sodium hydroxide, potassium hydroxide or ammoniacal liquor;
(4) hydrogen peroxide and dispersion precipitation again
Titanic Acid precipitation with superoxol dispersion steps again (3) becomes solution state, Ti:H
2O
2The molecule mole ratio be 1～8;
(5) adjust the pH value
Utilizing concentration is the pH value of the titanic acid solution of 30～60% mineral acid regulating step (4), requires to regulate corresponding pH value according to the finished product and can obtain corresponding product;
Described mineral acid is HNO
3, hydrochloric acid, sulfuric acid or phosphoric acid;
It is synthetic to be used for powder: pH＜1,
The dark red solution that this pH value condition obtains;
It is synthetic to be used for colloidal sol: pH=1～5,
This pH value condition obtains orange colloidal solution;
(6) preparation the finished product
In temperature is the solution 2～14 hours of 50～100 ℃ of following heating stepses (5) pH＜1, obtains oyster white colloidal sol, centrifugation or continuing heating can be settled out nano-titanium dioxide powder; Or be the solution 2～14 hours of 50～100 ℃ of heating stepses (5) pH=1～5 in temperature, obtain yellowish-orange transparent nano TiO 2 sol.
Described metatitanic acid compounds is selected from a kind of in barium titanate, strontium titanate, calcium titanate, magnesium titanate, aluminium titanates, zinc titanate, nickel titanate, metatitanic acid manganese, positive manganese titanate, metatitanic acid chromium, metatitanic acid cobalt or the positive cobalt titanate.
The nano-titanium dioxide powder that the present invention prepares or the purposes of colloidal sol
A) can be applied to high performance photocatalytic activity coating, the colloidal sol that the present invention prepares is verified to have good degradation of organic substances, the performance of kill bacteria.
B) can be used for pulling film forming and produce ecological ceramic, glass etc.
C) be used to handle after the cloth, can obtain having purifying air the textiles of kill bacteria effect.
D) can be at light fixture, area loads such as indoor plastic tub, thus have the effect of purifying air.
E) be used for the biological implantation material biological activity and handle, improve its biological fitness.
The performance that the product that utilizes the present invention to obtain has:
1. the about 15～30nm of TiO 2 sol particle diameter of the different-grain diameter that obtains, the pH value is neutral, and can stablize and preserve more than half a year, colloidal sol photocatalytic activity height,
2. the titanium dioxide powder particle that obtains is pure white, and particle diameter is about 40～60nm, can be at coating, and printing ink, papermaking, plastics, rubber is used as white pigment in the industry such as synthon.
The effect that the present invention has is:
1. directly at normal pressure, low temperature (50～100 ℃) synthesis nano TiO
2, greatly improved the Detitanium-ore-type traditional technology.
2. by method of the present invention, can be on same production line high performance nano titanic oxide sol of direct production and powder.
3. reaction conditions gentleness of the present invention is controlled the shape and the particle diameter of product easily, is to produce nano level TiO
2Splendid technology.
4. less demanding to the raw material grade, mineral resources (cheap starting material) is rich and easy to get.
5. the present invention has the plant and instrument of ready-made sulfuric acid process to use for reference on technology, and synthetic route is rationally superior, can carry out technology innovation on the synthetic titanium powder plant basis of the existing sulfuric acid process that falls behind.
Description of drawings
Fig. 1. the titanic oxide nano powder XRD spectra that the embodiment of the invention 2 obtains.
Fig. 2. the embodiment of the invention 3 titanium dioxide film degradation of methylene blue design sketchs.
Embodiment
Embodiment 1
Concentration is that (quality is than ilmenite: sulfuric acid=1:2) for 80% sulfuric acid heating for dissolving ilmenite, the solid precipitation thing that obtains obtains titanium liquid with water extraction, titanium liquid is removed by filter insoluble slag, and frozen recrystallization obtains titaniferous precursor solution to remove by filter ferrous sulfate; The pH value of regulating precursor solution with ammoniacal liquor is 7, obtains the titanic Acid precipitation.Get 80g titanic Acid precipitation and add the dissolving of 20ml30% superoxol, utilize 30%HNO
3Regulate pH=2, to 200ml, 100 ℃ of backflows obtained yellowish-orange transparent titanium dioxide nano colloidal sol in 6 hours with the gained solution dilution.
Embodiment 2
Make the titanic Acid precipitation with embodiment 1.Get 80g titanic Acid precipitation and add the dissolving of 20ml 30% superoxol, regulate pH=0.5 with 30% nitric acid, gained solution is diluted to 200ml with pure water, 100 ℃ of backflows obtained milky white precipitate in 6 hours, obtain nano-titanium dioxide powder after the vacuum-drying, the XRD spectra measurement result is confirmed that it is the anatase titanium dioxide crystal, sees accompanying drawing 1.
Embodiment 3
Concentration is 80% sulfuric acid heating for dissolving aluminium titanates, and the solid precipitation thing that obtains obtains titanium liquid with water extraction, and titanium liquid is removed by filter insoluble slag, and frozen recrystallization obtains titaniferous precursor solution to remove by filter Tai-Ace S 150; The heating precursor solution obtains the titanic Acid precipitation.Get 80g titanic Acid precipitation and add the dissolving of 20ml30% superoxol, utilize 30%HCl to regulate pH=2, to 200ml, 100 ℃ of backflows obtained yellowish-orange transparent titanium dioxide nano colloidal sol in 6 hours with the gained solution dilution.
Embodiment 4
The 100g titanyl sulfate is dissolved in and is made into titanium liquid in the 500ml distilled water, 1mol/lNaOH solution is regulated pH=7 and is obtained the titanic Acid precipitation, get 80g titanic Acid precipitation and add the dissolving of 20ml 30% superoxol, regulate pH=0.5 with 30% sulfuric acid, gained solution is diluted to 200ml with pure water, 100 ℃ of backflows obtained milky white precipitate in 6 hours, obtained nano-titanium dioxide powder after the vacuum-drying.
Embodiment 5
Make Nano sol with embodiment 1, in the clean glass surface film forming of supersound washing, intercepting 1 * 2cm width sheet glass was immersed in the 2mmol methylene blue solution after 24 hours by crystal pulling method, taking-up washes down with pure water, immerse 20ml 1mmol methylene blue solution, at 365nm, 1mW/cm
2Measure it under the ultraviolet lighting condition to the methylene blue degradation effect, measured the methylene blue solution ultra-violet absorption spectrum in per 20 minutes, confirm that the methylene blue pigment is had good degradation effect, see accompanying drawing 2.
Embodiment 6
Make Nano sol with embodiment 1, coat nano titanic oxide sol at ceramic surface by squeegee process, 100 ℃ of oven dry of baking oven obtain the finishing titanium dioxide layer.Antibacterial test confirms that intestinal bacteria can't survive on its surface.Simultaneously, drip methylene blue solution on the surface and obtain the blue trace that pollutes, through 365nm, 1mW/cm
2The blue trace that pollutes disappears behind the uv irradiating, confirms that obtained TiO 2 sol ceramic surface coating has antibiotic decontamination function.
Embodiment 7
Make Nano sol with embodiment 1, after 15cm * 15cm porous ceramics soaks 30min, 100 ℃ of oven dry appendix nano titanium oxide 3.24g in baking oven, 365nm, 1mW/cm
2Under the uv irradiating condition, the air cycle of forcing to contain formaldehyde at 80cm * 80cm * 100cm enclosed system this porous ceramics container of flowing through, the relative percentage concentration of formaldehyde drops to 7% by 100%, effectively therefore this type of obnoxious flavour of degraded can be widely used in airtight air circulation device gas sweetenings such as air-conditioning.
Embodiment 8
Make Nano sol with embodiment 1, soaked therewith in the colloidal sol 12 hours on 16cm * 13cm cotton cloth surface, 100 ℃ of oven dry appendix nano titanium oxide 0.14g in baking oven, antibacterial experiment confirms that it reaches more than 99% the intestinal bacteria killing effect, in 80cm * 80cm * 100cm contains the encloses container of formaldehyde air, with 365nm, 1m W/cm
2The uv irradiating cloth makes formaldehyde content be reduced to below the 0.5ppm by 2.5ppm, confirms to can be used for producing ecological cloth.
Claims (6)
1. the synthetic method of low temperature crystallized nano titanium dioxide powder or colloidal sol, it is characterized in that: this method may further comprise the steps:
(1) acidolysis
With sulfuric acid heating for dissolving ilmenite, the solid precipitation thing that obtains obtains titanium liquid with water extraction;
(2) titanium liquid purifies
The titanium liquid of step (1) is removed by filter insoluble slag, and frozen recrystallization removes by filter impurity, obtains titaniferous precursor solution;
(3) hydrating solution obtains the titanic Acid precipitation
The pH value that adds the titaniferous precursor solution of alkali neutralization procedure (2) is 5～11, obtains the titanic Acid precipitation;
Or the titaniferous precursor solution of dilution hydrolysing step (2), obtain the titanic Acid precipitation;
Or the titaniferous precursor solution of heating hydrolysis step (2), obtain the titanic Acid precipitation;
(4) hydrogen peroxide and dispersion precipitation again
Titanic Acid precipitation with superoxol dispersion steps again (3) becomes solution state, Ti:H
2O
2The molecule mole ratio be 1～8;
(5) adjust the pH value
Utilize pH＜1 of the titanic acid solution of mineral acid regulating step (4), it is synthetic to be used for powder; Or
Utilize pH=1～5 of the titanic acid solution of mineral acid regulating step (4), it is synthetic to be used for colloidal sol;
(6) preparation the finished product
In temperature is the solution of 50～100 ℃ of following heating stepses (5) pH＜1, obtains oyster white colloidal sol, centrifugation or continuing thermal precipitation goes out nano-titanium dioxide powder; Or
In temperature is the solution of 50～100 ℃ of following heating stepses (5) pH=1～5, obtains yellowish-orange transparent nano TiO 2 sol.
2. method according to claim 1 is characterized in that: described step (1) ilmenite: the vitriolic mass ratio is 1:2.
3. method according to claim 1 is characterized in that: the alkali of described step (3) is sodium hydroxide, potassium hydroxide or ammoniacal liquor.
4. method according to claim 1 is characterized in that: the mineral acid that described step (5) is adjusted the pH value is HNO
3, hydrochloric acid, sulfuric acid or phosphoric acid.
5. method according to claim 1 is characterized in that: described nano titanic oxide sol particle diameter is 15～30nm.
6. method according to claim 1 is characterized in that: described nano-titanium dioxide powder particle grain size is 40～60nm.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1373089A (en) * | 2002-02-01 | 2002-10-09 | 武汉大学 | Process for preparing anatase-phase nano TiO2 |
| CN1431154A (en) * | 2003-02-12 | 2003-07-23 | 邓昭平 | Method for preparing liquid state predecessor of nano titanium dioxide |
| CN1530326A (en) * | 2003-03-13 | 2004-09-22 | 中国科学院化学研究所 | Normal temperature solidified titania sol |
| CN1609000A (en) * | 2003-10-17 | 2005-04-27 | 胡祥 | Prepn process of nano filming titanium dioxide colloid |
| JP2005162554A (en) * | 2003-12-04 | 2005-06-23 | Sundecor:Kk | Method for producing titania solution |
-
2005
- 2005-09-22 CN CNB2005101048244A patent/CN100484880C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1373089A (en) * | 2002-02-01 | 2002-10-09 | 武汉大学 | Process for preparing anatase-phase nano TiO2 |
| CN1431154A (en) * | 2003-02-12 | 2003-07-23 | 邓昭平 | Method for preparing liquid state predecessor of nano titanium dioxide |
| CN1530326A (en) * | 2003-03-13 | 2004-09-22 | 中国科学院化学研究所 | Normal temperature solidified titania sol |
| CN1609000A (en) * | 2003-10-17 | 2005-04-27 | 胡祥 | Prepn process of nano filming titanium dioxide colloid |
| JP2005162554A (en) * | 2003-12-04 | 2005-06-23 | Sundecor:Kk | Method for producing titania solution |
Non-Patent Citations (1)
| Title |
|---|
| Photocatalytic Activities of Coating Films Prepared fromPeroxotitanic Acid Solution-Derived Anatase Sols,. Hiromichi Ichinose, et al.Journal of the Ceramic Society of Japan,Vol.106 No.3. 1998 * |
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