CN115304098A - Nano titanium dioxide - Google Patents
Nano titanium dioxide Download PDFInfo
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- CN115304098A CN115304098A CN202211141489.5A CN202211141489A CN115304098A CN 115304098 A CN115304098 A CN 115304098A CN 202211141489 A CN202211141489 A CN 202211141489A CN 115304098 A CN115304098 A CN 115304098A
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- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000005406 washing Methods 0.000 claims abstract description 13
- 238000003825 pressing Methods 0.000 claims abstract description 7
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 239000003630 growth substance Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 16
- 239000013078 crystal Substances 0.000 claims description 15
- 239000012065 filter cake Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000000460 chlorine Substances 0.000 claims description 9
- 210000003298 dental enamel Anatomy 0.000 claims description 8
- 239000012716 precipitator Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 230000001376 precipitating effect Effects 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 238000004537 pulping Methods 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 238000010009 beating Methods 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000012452 mother liquor Substances 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 abstract description 17
- 238000002360 preparation method Methods 0.000 abstract description 14
- 239000000047 product Substances 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 abstract description 2
- 239000003337 fertilizer Substances 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 9
- 230000032683 aging Effects 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- -1 ammonium ions Chemical class 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000001016 Ostwald ripening Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- ZHIIUGIVMJPBFB-UHFFFAOYSA-N azane;ethene Chemical compound N.N.C=C ZHIIUGIVMJPBFB-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
- C01G23/0536—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing chloride-containing salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/16—Halides of ammonium
- C01C1/164—Ammonium chloride
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides nano titanium dioxide, and belongs to the technical field of material synthesis. The nano titanium dioxide provided by the invention has a rod-shaped micro morphology, the rutile phase proportion of the nano titanium dioxide is more than or equal to 99%, and the specific surface area is 20-130m 2 Controllable in the range of/g. The invention provides a rod-shaped rutile TiO 2 The preparation method has simple operation process and mild reaction condition, and can realize industrial production. The method has great advantages in raw material cost, avoids the difficulties of post-treatment of organic solvent and introduction of magnetic substances in the product, and improves the purity of the product. The method also realizes green utilization of each element, and byproduct NH 4 Washing, filter pressing, concentrating, cooling and crystallizing Cl to finally obtain NH used in the field of agricultural fertilizers 4 Cl is crystallized, and the production idea of green chemistry is realized.
Description
Technical Field
The invention belongs to the technical field of material synthesis, relates to nano titanium dioxide, and particularly relates to rod-shaped rutile type nano titanium dioxide.
Background
TiO 2 Is an important inorganic non-metallic material with excellent properties, which can be divided into three structures of rutile, anatase and brookite, wherein the former two are tetragonal system, the latter is orthorhombic system, and the rutile type TiO is 2 Stable structure and wide application range, and the preparation process is concerned by researchers.
At present, tiO 2 The preparation method mainly comprises a gas phase reaction method, a solid phase reaction method and a liquid phase reaction method. The gas phase method can generate high temperature due to the process, the produced by-product can seriously corrode equipment, and the preparation cost of the product is high, so the industrial production application is less. The solid phase method has simple preparation process, but the obtained TiO 2 The particle size distribution is relatively wide, and the material quality is extremely rough. The liquid phase method has the advantages of the two methods, avoids the disadvantages, has mild reaction conditions, simple equipment requirements and low cost, and is suitable for industrial production.
The shape of the nano material has profound influence on the performance of the nano material, namely rod-shaped TiO 2 So that it exhibits excellent properties in terms of electron transport and photocatalysis, and thus, rod-shaped TiO 2 Has great practical significance in the fields of energy sources and photocatalysis.
CN105967229A describes a method of preparing a solution from a titanium source and an organic solvent, stirring uniformly, pouring into a reaction kettle, performing a hydrothermal reaction at 60-300 ℃ for 6-36 hours, then centrifugally washing a hydrothermal product with deionized water or ethanol, and finally drying and calcining the product to obtain rod-like titanium dioxide. The method needs high pressure, high temperature and longer heat preservation time, greatly increases the cost of industrial production and preparation, and is accompanied with the use and treatment procedures of organic matters in the production process. CN105016382A describes a method for preparing rutile type nanometer TiO with controllable morphology by using hydrolysis reaction of titanium source substance under the conditions of normal pressure and lower temperature, using water as dispersion medium and 0.5% -50% of the weight of titanium source as iron-containing crystal form control agent 2 The method of (1). The method adopts normal pressure and low temperature production processThe requirement of equipment and the cost reduction have obvious effect, but the adoption of the iron-containing crystal form control agent can introduce metal impurities into the product, thereby greatly limiting the TiO product 2 And increases the hazard in catalysts, battery electrode additives.
Disclosure of Invention
The invention provides a nano titanium dioxide and a prepared TiO 2 Uniform particle size, good dispersibility, rutile phase ratio of more than 99%, and specific surface area of 20-130m 2 Controllable in the range of/g, greatly broadens TiO 2 The field of application of (1).
In order to achieve the aim, the invention provides nano titanium dioxide which has a rod-shaped micro morphology, has a rutile phase ratio of more than or equal to 99 percent and has a thickness of 20-130m 2 Specific surface energy per gram.
Preferably, tiCl is used 4 The titanium source is prepared by taking water with the temperature of 80-90 ℃ as a medium, adding a proper amount of precipitator and growth regulator and adopting a coprecipitation method.
Preferably, the precipitant is at least one selected from polyacrylic acid, ammonium polyacrylate, sodium polyacrylate, urea and ethylenediamine tetraacetic acid; the growth regulator is at least one selected from cetyl trimethyl ammonium bromide, N-dimethylformamide, polyethyl diammonium and ammonia water.
Preferably, the nano titanium dioxide is prepared by the following method:
adding pure water and a precipitator into a reaction kettle in sequence, heating to 80-90 ℃, then continuously stirring for 30-50 min, adding a growth regulator 10-15min before putting into reaction, and preparing a reaction kettle base solution;
mixing the prepared TiCl 4 The solution is added into the bottom solution of the reaction kettle at a preset dripping speed, the temperature of the reaction kettle is controlled between 80 and 90 ℃, and the temperature is kept for 1.5 to 2.5 hours after the feeding is finished;
after the temperature of the reaction kettle is kept to be lower than 70 ℃, the stirring is closed, the reaction kettle is kept still for 1 to 2 hours, and primary crystal precipitation is carried out;
heating the system in the reaction kettle to 100-115 ℃, boiling the water and dissolving the unreacted raw materials wrapped on the surface of the crystal into the water again;
when the temperature of the reaction kettle is reduced to below 70 ℃ again, the stirring is closed, the reaction kettle is kept still for 1 to 2 hours, and secondary crystal precipitation is carried out;
filter pressing solid-liquid separation, putting the filter cake into a pulping kettle, pulping and dispersing, diluting the residual mother liquor in the filter cake into water for washing to remove chlorine, filter pressing solid-liquid separation again to obtain pure metatitanic acid TiO (OH) 2 A filter cake;
calcining the obtained filter cake for 3-4h at the temperature of above 500 ℃ to obtain the rod-shaped rutile type nano titanium dioxide.
In the scheme, the bottom solution of the reaction kettle is prepared by synthesizing rod-shaped rutile TiO 2 One of the key steps of (1). Specifically, tiCl is promoted by adding a precipitant into pure water in a reaction kettle 4 The hydrolysis process effectively avoids the situation that the hydrolysis tends to be balanced in a strong acid environment, which leads to metatitanic acid TiO (OH) 2 The existing of the precipitating agent simultaneously plays a role of flocculation, so that the products are interacted, and the solid-liquid separation of the subsequent filter pressing process is facilitated.
Meanwhile, the growth regulator is added in the step of synthesizing rod-shaped rutile TiO 2 The second critical step of (1). Specifically, in a supersaturated system, nucleation begins when the system energy reaches a certain value. The change of new nuclei during crystallization depends on the size of the nuclei, which can be dissolved and grow as the free energy decreases, and generally larger grains undergo crystal growth by consuming other small grains, which phenomenon can be attributed to the ostwald ripening mechanism. The action mechanism of the high molecular polymer containing the ammonium ions is that the ammonium ions have a pair of lone-pair electrons, and empty tracks exist on the electron arrangement of the metal Ti valence layer, so that the two are easy to attract each other to form a complex; the high molecular polymer is distributed in the solution system like a net, and ammonium ions are compared with knots on the net, so that TiO (OH) is separated out from the system 2 Will be firmly bound in a small grid, avoiding OsterThe occurrence of Walder ripening phenomena, the spatial network defining the TiO (OH) 2 So as to finally form a rod-shaped TiO with good dispersibility 2 The precursor of (1).
In addition, in the above steps, the water boiling and secondary aging step is to synthesize rod-shaped rutile type TiO 2 The third key step of (1). In particular, tiO (OH) 2 In the crystallization process, the most stable crystal form cannot be directly generated, but an unstable crystal form is generated firstly, then the crystal form is gradually changed to a more stable crystal form along with the continuous increase (decrease) of the temperature and the lapse of time, and the rod-shaped TiO with the rutile phase ratio of more than 99 percent is finally obtained through repeated aging, temperature rise and aging and the prolonging of the heat preservation time 2 。
Preferably, the mass ratio of the pure water, the precipitating agent and the growth regulator added is 1: (0.01-0.1): (0.02-0.05).
Preferably, tiCl is used 4 The solution is added into a reaction kettle at the dropping speed of 20 to 33L/min, wherein TiCl 4 The mass ratio of the solution to water is 1: (0.5-0.8). It is understood that TiCl is added 4 The mass ratio of the solution to water may be specifically 1:0.5, 1:0.6, 1:0.7, 1:0.8 or any other ratio within the above range. TiCl (titanium dioxide) 4 Specifically, the solution may be fed into the reaction vessel at 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33L/min or any other dropping rate within the above range. Preferably, it can be driven into the reaction kettle by means of an air operated diaphragm pump.
Preferably, tiCl 4 The solution was prepared by the following method:
adding pure water into an enamel kettle with a condensation jacket, starting stirring, and adding pure TiCl 4 Slowly dripping into enamel kettle, and stirring for 80-100 min.
Preferably, pure TiCl is added at 25 ℃ 4 Dripping into enamel kettle at dripping speed of 8-15L/min, wherein TiCl 4 The mass ratio of the pure water to the pure water is 1: (1-1.8). It will be appreciated that TiCl is added 4 The mass ratio of the solution to the pure water may be specifically 1:1. 1:1.1. 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8 or any other ratio within the above range. TiCl (titanium dioxide) 4 Specifically, the solution may be fed into the reaction vessel at 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18L/min or any other dropping rate within the above range. Preferably, it can be driven into the reaction kettle by means of an air operated diaphragm pump.
Preferably, when the solid-liquid separation and the washing with water are performed to remove chlorine, the cake is formed by performing the center washing and the diagonal washing.
Preferably, the beating dispersion is carried out for at least 2 times, warm water with the mass 5-10 times that of the filter cake is added during each beating dispersion, and the conductivity of the final filter-pressed effluent is controlled to be less than or equal to 100us/cm.
Compared with the prior art, the invention has the advantages and positive effects that:
1. the invention provides a rod-shaped rutile TiO 2 The preparation method has simple operation process and mild reaction condition, can realize industrial production, and the prepared TiO 2 Uniform particle size, good dispersibility, rutile phase ratio of more than 99%, and specific surface energy of 20-130m 2 Controllable production in the range of/g, greatly broadens TiO 2 The field of application of (1).
2. The TiO provided by the invention 2 In the preparation method, tiCl4 is used as a titanium source, water is used as a reaction medium, so that the use of an organic solvent is avoided, great advantages are achieved in the aspect of raw material cost, and the problem of post-treatment of the organic solvent is avoided; the invention takes the ammonium compounds and the high molecular compounds as additives to replace crystal form control agents containing metal elements, avoids introducing magnetic substances into the product and improves the purity of the product.
3. The invention realizes the green utilization of each element and the byproduct NH 4 Washing, filter pressing, concentrating, cooling and crystallizing Cl to finally obtain NH which can be used in the field of agricultural fertilizers 4 Cl is crystallized, and the production idea of green chemistry is realized.
Drawings
FIG. 1 shows a rod-like rutile TiO provided in an embodiment of the present invention 2 SEM characterization of (d);
FIG. 2 shows a rod-like rutile TiO compound provided in an embodiment of the present invention 2 XRD characterization pattern of (a).
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Adding 600L of pure water into an enamel kettle, and taking pure TiCl 4 The solution is 400L, condensed water is started, and pure TiCl is dripped into the enamel kettle while stirring 4 The dropping speed of the solution was controlled at 9.0L/min. After the charging is finished, stirring for 90min to obtain TiCl 4 A solution;
adding 500L of pure water into a synthesis kettle, and adding a precipitator A, wherein the precipitator is a mixture of polyacrylamide and urea, and the mass ratio of the precipitator to the precipitator is 1:1.5, the weight of the precipitant A is 5kg. The temperature is raised to 85 ℃ while stirring, after the precipitant is completely dissolved, the growth regulator B is added before the reaction, and the growth regulator is the poly (ethylene diammonium) with the weight of 15kg. Stirring for 5 min;
starting the synthesis kettle for stirring, and using a pneumatic diaphragm pump to mix TiCl 4 Dropwise adding the solution into a synthesis kettle containing a base solution at a speed of 25L/min, controlling the reaction temperature at 85 ℃ after the feeding is finished, and keeping the temperature for 1.5h;
after the reaction is finished, reducing the temperature of the reaction kettle to 65 ℃, stopping stirring, and standing and aging for 1h; then starting stirring, raising the temperature of the reaction kettle to 100 ℃, and boiling for 1h; after the water boiling is finished, reducing the temperature of the reaction kettle to 65 ℃, and performing secondary aging for 1h;
separating metatitanic acid from the slurry in the reaction kettle by using a filter press, repeatedly pulping the separated filter cake to filter and fully filter Cl - Washing out;
will wash Cl - The filter cake passes through a roller kiln at 50 DEG CCalcining at 0 ℃ to obtain rod-shaped rutile TiO 2 . The obtained rod-like rutile type TiO 2 The SEM characteristic diagram and the XRD characteristic diagram are shown in figures 1-2.
Example 2
The preparation method is the same as example 1, except that the added precipitating agent is sodium polyacrylate, the growth regulator is N, N-dimethylformamide, and the rest differences are shown in Table 1.
Example 3
The preparation method is the same as example 1, except that the added precipitating agent is ethylenediamine tetraacetic acid, the growth regulator is cetyltrimethylammonium bromide, and the rest differences are shown in table 1.
Example 4
The preparation method is the same as example 1, except that the added precipitating agent is ammonium polyacrylate, the growth regulator is ammonia water, and the rest differences are shown in Table 1.
Comparative examples 1 to 7
The preparation method is the same as that of example 1, and the difference between the precipitant and the growth regulator is shown in Table 1.
Comparative example 8
The preparation method is the same as example 1, and the parameter settings are the same as example 1, except that the used precipitating agent is polyacrylamide.
Comparative example 9
The preparation method is the same as example 1, and the parameter settings are the same as example 1, except that the growth regulator used is dodecyl trimethyl ammonium bromide.
TABLE 1 setting of the parameters of examples 1 to 4 and comparative examples 1 to 9 and the TiO obtained 2 Physical characterization
As can be seen from the data in Table 1, the use of a combination of a precipitant and a growth regulator helps to increase the rutile phase ratio androd-like micro-morphology TiO 2 Synthesizing; the reaction time is prolonged, the aging crystallization frequency is increased, the rutile crystal phase ratio is improved, and the TiO is directly influenced by the type of the growth regulator 2 The microscopic morphology of (a); and multiple pulping and washing are beneficial to removing TiO 2 Cl of - The purity of the rutile phase is improved, and the rutile phase accounts for more than 99%.
Claims (10)
1. The nanometer titanium dioxide is characterized in that the nanometer titanium dioxide has a rod-shaped micro-morphology, the rutile phase accounts for more than or equal to 99 percent, and the specific surface area is 20-130m 2 Controllable in the range of/g.
2. The nano-titanium dioxide as claimed in claim 1, wherein TiCl is used 4 The titanium source is prepared by taking water with the temperature of 80-90 ℃ as a medium, adding a proper amount of precipitator and growth regulator and adopting a coprecipitation method.
3. The nano titanium dioxide according to claim 2, wherein the precipitating agent is selected from at least one of polyacrylic acid, polyacrylamide, sodium polyacrylate, urea and ethylenediaminetetraacetic acid; the growth regulator is at least one selected from cetyl trimethyl ammonium bromide, N-dimethylformamide, polyethyl diammonium and ammonia water.
4. The nano titanium dioxide according to any one of claims 1 to 3, wherein the nano titanium dioxide is prepared by the following method:
adding pure water and a precipitator into a reaction kettle in sequence, heating to 80-90 ℃, then continuously stirring for 30-50 min, adding a growth regulator 10-15min before putting into reaction, and preparing a reaction kettle base solution;
mixing the prepared TiCl 4 The solution is added into the bottom solution of the reaction kettle at a preset dripping speed, the temperature of the reaction kettle is controlled between 80 and 90 ℃, and the temperature is kept for 1.5 to 2.5 hours after the feeding is finished;
after the temperature of the reaction kettle is kept to be lower than 70 ℃, the stirring is closed, the reaction kettle is kept still for 1 to 2 hours, and primary crystal precipitation is carried out;
heating the system in the reaction kettle to 100-115 ℃, boiling the water and dissolving the unreacted raw materials coated on the surface of the crystal into the water again;
when the temperature of the reaction kettle is reduced to below 70 ℃ again, the stirring is closed, the reaction kettle is kept still for 1 to 2 hours, and secondary crystal precipitation is carried out;
filter pressing solid-liquid separation, putting the filter cake into a pulping kettle, pulping and dispersing, diluting the residual mother liquor in the filter cake into water for washing to remove chlorine, filter pressing solid-liquid separation again to obtain pure metatitanic acid TiO (OH) 2 A filter cake;
calcining the obtained filter cake for 3-4h at the temperature of more than 500 ℃ to obtain the rod-shaped rutile type nano titanium dioxide.
5. The nano titanium dioxide as claimed in claim 4, wherein the mass ratio of the added pure water, the precipitant and the growth regulator is 1: (0.01-0.1): (0.02-0.05).
6. The nano titanium dioxide as claimed in claim 4, wherein the TiCl is reacted with the titanium oxide 4 The solution is added into a reaction kettle at the dropping speed of 20 to 33L/min, wherein TiCl 4 The mass ratio of the solution to water is 1: (0.5-0.8).
7. The nano titanium dioxide as claimed in claim 4, wherein TiCl is 4 The solution was prepared by the following method:
adding pure water into an enamel kettle with a condensation jacket, starting stirring, and adding pure TiCl 4 Slowly dripping into enamel kettle, and stirring for 80-100 min.
8. The nano-titanium dioxide as claimed in claim 7, wherein pure TiCl is added at 25 ℃ 4 Dripping into enamel kettle at dripping speed of 8-15L/min, wherein TiCl 4 The mass ratio of the pure water to the pure water is 1: (1-1.8).
9. The nano titanium dioxide as claimed in claim 4, wherein the solid-liquid separation and the water washing for chlorine removal are carried out by performing a center washing and a diagonal washing in the formation of a filter cake.
10. The nano titanium dioxide as claimed in claim 4, wherein the beating dispersion is carried out at least 2 times, warm water with the mass 5-10 times of that of a filter cake is added during each beating dispersion, and the conductivity of final filter-pressed effluent is controlled to be less than or equal to 100us/cm.
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