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Publication numberCN103120933 A
Publication typeApplication
Application numberCN 201110369778
Publication date29 May 2013
Filing date18 Nov 2011
Priority date18 Nov 2011
Publication number201110369778.6, CN 103120933 A, CN 103120933A, CN 201110369778, CN-A-103120933, CN103120933 A, CN103120933A, CN201110369778, CN201110369778.6
Inventors唐康健, 杨为民, 朱俊华, 程远琳, 王黎敏
Applicant中国石油化工股份有限公司, 中国石油化工股份有限公司上海石油化工研究院
Export CitationBiBTeX, EndNote, RefMan
External Links: SIPO, Espacenet
Preparation method of nanometer TiO2/ZrO2 composite material
CN 103120933 A
Abstract
The invention relates to a preparation method of a nanometer TiO2/ZrO2 composite material, mainly aiming at solving the problems of an existing synthetic technology that the process is complicated, the Ti-Zr composite degree is low, and the product grain diameter is large. The preparation method provided by the invention adopts the technical scheme that the water vapor is adopted to hydrolyze an organic titanium and zirconium solution, the problems are preferably solved, and the preparation method can be used in industrial production of the nanometer TiO2/ZrO2 composite material with high loading titanium quantity.
Claims(5)  translated from Chinese
1.一种纳米Ti02/Zr02复合材料的制备方法,包括以下步骤:a)将有机钛和有机锆分散于高于水沸点的有机溶剂中得到混合液I,混合液I中Ti: Zr的摩尔比为0.01〜100:1 ;钛与锆的总摩尔数与有机溶剂的摩尔数比为0.01〜100:1 ;b)在100〜240C条件下,使水蒸气与混合液I相接触,使混合液I中的有机钛与有机锆同时发生水解反应,得到纳米Ti02/Zr02复合材料的前体II ;c)在300〜1000C条件下将前体II焙烧4〜72小时得纳米Ti02/Zr02复合材料。 A nano-Ti02 / Zr02 composite material, comprising the steps of: a) an organic titanium and organic zirconium higher than the boiling point of water is dispersed in an organic solvent to give a mixture I, mixture I, Ti: Zr molar 0.01~100 ratio: 1; the number of moles on the total moles of titanium and zirconium and an organic solvent is 0.01~100: 1; b) at 100~240 C conditions, a mixture of steam and I make contact, I make a mixture of an organic titanium and organic zirconium hydrolysis reaction simultaneously to obtain nanometer Ti02 / Zr02 composite precursor II; c) the conditions under 300~1000 C calcined precursor II 4~72 hours nano Ti02 / Zr02 composites.
2.根据权利要求1所述纳米Ti02/Zr02复合材料的制备方法,其特征在于钛源选自醇钛或钛酸酯的有机钛中的至少一种。 1 2. The method of nano Ti02 / Zr02 composite according to claim, characterized in that the at least one titanium source is selected from titanium alkoxide or an organic titanate of titanium.
3.根据权利要求1所述纳米Ti02/Zr02复合材料的制备方法,其特征在于锆源选自醇锆或锆酸酯等有机锆中的至少一种。 1 3. The method of nano Ti02 / Zr02 composite according to claim, wherein the zirconium source is selected from alcohols of at least one organic zirconate, zirconium or zirconium.
4.根据权利要求1所述纳米Ti02/Zr02复合材料的制备方法,其特征在于有机溶剂为难溶解水的弱极性溶剂。 4. The method according nano Ti02 / Zr02 Composite according to claim, characterized in that the organic solvent difficult to dissolve water weakly polar solvent.
5.根据权利要求1所述纳米Ti02/Zr02复合材料的制备方法,其特征在于反应温度为.80 〜260℃。 5. The method according nano Ti02 / Zr02 composite according to claim, characterized in that the reaction temperature is from .80 ~260 ℃.
Description  translated from Chinese

纳米Ti02/Zr02复合材料的制备方法 Nano Ti02 / Zr02 of composite material

技术领域 Technical Field

[0001] 本发明涉及一种纳米Ti02/Zr02复合材料的制备方法。 [0001] The present invention relates to a method for preparing nanometer Ti02 / Zr02 composites.

背景技术 Background

[0002]四价的金属低维纳米氧化物Ti02、ZrO2,有着极其广泛的应用领域。 [0002] Low-dimensional metal oxide tetravalent Ti02, ZrO2, has an extremely wide range of applications. 二氧化钛(TiO2)是世界上最重要的性能最佳的白色颜料。 Titanium dioxide (TiO2) is the world's best performance of the most important white pigment. 广泛应用于涂料,造纸,化纤塑料,橡胶医药,化妆品,电子元件,冶金光催化剂等二十多个行业。 Widely used in more than 20 industries in paint, paper, synthetic plastic, rubber medicine, cosmetics, electronic components, metallurgy light catalyst. 纳米二氧化钛作为一种新型光催化齐U,抗紫外线剂,光电效应剂等,将以其神奇的功能在环境,信息材料,能源医疗与卫生等领域的技术革命中起到不可低估的作用。 Nano-titanium dioxide as a novel photocatalytic Qi U, anti-UV agents, the photoelectric effect and the like, will be its fantastic features play an incomparable role in the technological revolution environment, information materials, energy, medical and health fields in. 纳米二氧化钛有吸收紫外线的功能,它在全部紫外线光区(UVC+UVB+UVA)都具有有效的紫外线滤除能力。 Nano-titanium dioxide absorbs UV features, it has the ability to effective UV filter out all UV light district (UVC + UVB + UVA). 当前,纳米TiO2的光催化研究可用于有机物贵金属回收以及对废水和空气中有机污染物,另外纳米TiO2还能使微生物细菌等分解成CO2和H2O起到灭菌除臭防污自洁的效果。 Currently, Nano TiO2 light catalysis research can be used in organic wastewater and the recovery of precious metals and organic pollutants in the air, in addition to the nano TiO2 can make bacteria and other micro-organisms break down into CO2 and H2O play sterilization deodorant anti-fouling and self-cleaning effect. 锆与钛为同主族元素,而锆比钛多了一个周期,更显现出其金属特性,广泛应用于陶瓷技术;异种催化;含有ZrO2的特种陶瓷材料是电子、航天、航空和核工业的基础材料,其独特的酸碱稳定性使其在石蜡工业(异构化,脱氢等)极有价值。 Zirconium and titanium for the same main group elements, zirconium and titanium more than one cycle, more show its metallic properties, widely used in ceramic technology; heterogeneous catalysis; special ceramic material containing ZrO2 are electronics, aerospace, aviation and nuclear industry basic materials, which make it unique pH stability paraffin industry (isomerization, dehydrogenation, etc.) extremely valuable. 纳米级的ZrO2更被广泛应用于特种陶瓷;陶瓷薄膜;复合多相催化剂等方面。 Nanoscale ZrO2 more widely used in special ceramics; and other aspects of complex heterogeneous catalysts; ceramic film. 近年来,对Ti02/Zr02的二元纳米复合材料研究日趋升温,该二元材料表现出T 比纯TiO2 更高的光催化性质[X.Fu, LAClark, Q.Yang, MA.Anderson, Environ.Sc1.Technol.1996,30,647.],并且Ti02/Zr02的复合材料还有着更大的表面积和更强的酸碱性质[J.Miciukiewicz, T.Mang, Appl.Catal.A:Gen.1995,122,151.]。 In recent years, binary nanocomposite Ti02 / Zr02 research becomes hot, the binary material exhibits a T higher than that of pure TiO2 photocatalytic properties [X.Fu, LAClark, Q.Yang, MA.Anderson, Environ. Sc1.Technol.1996,30,647], and the composite material Ti02 / Zr02 there a greater surface area and a stronger acid nature [J.Miciukiewicz, T.Mang, Appl.Catal.A:. Gen.1995 , 122,151.]. 它已经广泛应用于汽车尾气中NOx的脱除[丁光辉,蒋晓原,林年达,化学通报2003,66(10):673.]、燃料的加氢脱硫[Daly FP,Ando H.,Schmitt JL,J.Catal.1987,108(2):401.]、氟氯烃脱除[Tajima M.,Niwa M.,Fujii Y.,Appl.Catal.B 1997,14(1-2):97.]等环保领域以及环己酮肟的气相Beckmann重排、加氢及氢处理等重要的催化反应。 It has been widely used in automotive exhaust NOx removal [Ding Guanghui, JIANG Xiao Yuan, Lin amounted chemical Bulletin 2003,66 (10): 673], hydrodesulfurization of fuel [Daly FP, Ando H., Schmitt JL , J.Catal.1987,108 (2):. 401], HCFC removal [Tajima M., Niwa M., Fujii Y., Appl.Catal.B 1997,14 (1-2): 97. ] and other environmental fields as well as important catalytic reaction of cyclohexanone oxime vapor phase Beckmann rearrangement, hydrogenation, and hydrogen processing.

[0003] 制备该二元纳米Ti02/Zr02复合材料的方法很多,归纳起来基本包括二种,气相法与液相法:气相化学反应可分为三类=TiCl4, ZrOCl2与O2氧化;醇钛,醇锆盐直接热裂解;醇钛、醇锆盐气溶胶气相分解。 [0003] The process for preparing the binary Nano Ti02 / Zr02 Composite many, summed up basically comprises two kinds of gas-phase and liquid-phase method: gas-phase chemical reaction can be divided into three categories = TiCl4, ZrOCl2 and O2 oxidation; alcohol titanium, Direct thermal cracking alcohol zirconium salts; alcohol titanium, zirconium salt aerosol alcohol vapor decomposition. 液相反应中醇钛盐sol-gel法和TiCl4, ZrOCl2惰气保护水解方法。 Liquid phase reaction alcohol titanium salt sol-gel method and TiCl4, ZrOCl2 hydrolysis inert gas protection. 综上所述,现有用于制备Ti02/Zr02复合材料的技术中要么陈旧,要么复杂。 In summary, the existing prepared for Ti02 / Zr02 composite material is either obsolete or complex. 这些因素大大地限制了Ti02/Zr02复合材料的发展及工业应用。 These factors greatly limit the Ti02 / Zr02 composite materials development and industrial applications.

发明内容 DISCLOSURE

[0004] 本发明所要解决的技术问题是现有合成技术中存在的过程复杂、钛锆复合程度低,产品粒径大的问题,提供一种新的纳米级Ti02/Zr02复合材料的制备方法。 [0004] The technical problem to be solved by the present invention is a process of the prior art that the synthesis of complex, low-level titanium-zirconium composite product size big problem, providing a new nano-Ti02 / Zr02 preparing composites. 该方法具有简洁、高效,能避免毛细凝聚作用所导致的纳米结块问题,并且所得Ti02/Zr02复合材料具有复合好,粒径小于10纳米的优点。 This method has the simple, efficient, can prevent capillary condensation effect of nano-caking problems caused and the resulting Ti02 / Zr02 composite has good composite particle size less than 10 nanometers advantages.

[0005] 为解决上述技术问题,本发明采用的技术方案如下:一种纳米Ti02/Zr02复合材料的制备方法,包括以下步骤:a)将有机钛和有机锆分散于高于水沸点的有机溶剂中得到混合液I,混合液I中Ti: Zr的摩尔比为0.01〜100: I ;钛与锆的总摩尔数与有机溶剂的摩尔数比为0.01〜100:1 ;b)在100〜240C条件下,使水蒸气与混合液I相接触,使混合液I中的有机钛与有机锆同时发生水解反应,得到纳米Ti02/Zr02复合材料的前体II ;c)在300〜1000C条件下将前体II焙烧4〜72小时得Ti02/Zr02复合材料。 [0005] In order to solve the above problems, the technical aspect of the present invention is used as follows: A method for preparing nanometer Ti02 / Zr02 composite, comprising the steps of: a) an organic titanium and organic zirconium higher than the boiling point of water is dispersed in an organic solvent The obtained mixture I, mixture I, Ti: Zr molar ratio is 0.01~100: I; number of moles of the total moles of titanium, and zirconium with an organic solvent is 0.01~100: 1; b) at 100~240 C under conditions in which water vapor is contacted with a mixture of I, I make the mixture with the organic zirconium organotitanium simultaneous hydrolysis reaction, to obtain a nano Ti02 / Zr02 composite precursor II; c) at 300~1000 conditions under C 4~72 hours firing precursor II was Ti02 / Zr02 composites.

[0006] 上述技术方案中,钛源优选方案自醇钛或钛酯的有机钛中的至少一种;锆源优选方案选自醇锆或锆酯的有机锆中的至少一种。 [0006] In the above aspect, since the titanium source is preferably at least one alcohol solution of titanium or a titanium ester in an organic titanium; zirconium source is preferably selected from an alcohol solution of at least one organic zirconium or zirconium in the zirconium esters. 有机溶剂优选方案为难溶水的弱极性溶剂,反应温度优选范围为100〜240C。 The organic solvent is preferably water insoluble solution for weakly polar solvent, the reaction temperature is preferably in the range of 100~240 C.

[0007] 通过上述技术方案,有效避免了毛细凝聚作用所导致的纳米结块问题,且不需要添加任何模板剂,阻聚剂,大大降低了反应的复杂性和成本。 [0007] The above technical solution to effectively prevent the agglomeration of nano capillary condensation problems caused by, and do not need to add any template, polymerization inhibitors, which greatly reduces the complexity and cost of response. 本发明中由于使用水蒸气水解有机溶液的方法在反应器中制备纳米Ti02/Zr02复合材料,水解前,钛锆有机源原子级充分接触,晶化后,得到的产品粒径只有几个纳米。 The present invention is the use of water vapor hydrolysis of the organic solution in the reactor Nano Ti02 / Zr02 composites, prior to hydrolysis, titanium, zirconium organic source atomic level full contact, after crystallization, the resulting product particle size of a few nanometers. 由于产品粒径只有几个纳米,大大增加了TiO2与ZrO2之间的相互作用,复合程度极高。 As the product is only a few nanometers in diameter, greatly increasing the interaction between TiO2 and ZrO2, highly complex level. 另外,本发明方法中由于不含有任何模板剂,大大降低了成本,取得了较好的技术效果。 In addition, the method of the present invention, because they do not contain any template, significantly reducing costs, achieved good technical results.

附图说明 Brief Description

[0008] 图1为所制备的纳米Ti02/Zr02复合材料(T1: Zr = 1: 15〜15: 1)600C焙烧后的X射线衍射谱图。 [0008] FIG. 1 is a nanometer prepared Ti02 / Zr02 Composite (T1: Zr = 1: 1: 15~15) X-ray diffraction pattern of the calcined 600 C.

[0009] 图2为所制备的纳米Ti02/Zr02复合材料(T1: Zr = 1: 15〜15: 1)600C焙烧后的紫外吸收谱(UV)图。 [0009] FIG. 2 is prepared nanometer Ti02 / Zr02 composite (T1: Zr = 1: 15~15: 1) UV-600 C calcined absorption spectrum (UV) FIG.

[0010] 图3为所制备的纳米1102/21<)2复合材料(Ti: Zr = I: I)600C焙烧后的紫投射电镜(TEM)图。 [0010] FIG. 3 is prepared nanometer 1102/21 <) 2 composite (Ti: Zr = I: I) 600 C calcined violet transmission electron microscopy (TEM) in FIG.

[0011] 在图1中,XRD谱峰明显宽化,表明制备的Ti02/Zr02复合材料为纳米晶。 [0011] In Figure 1, XRD peak broadening significantly, indicating Ti02 / Zr02 composite material for nanocrystals. 其中谱线C,(在T1: Zr = 1:1 情况下),显现出两者的完美复合。 Wherein the line C, (in T1: Zr = 1: 1 case), showing perfect composite of both. 即XRD没有显现出任何单独一种氧化物的特征谱线。 That XRD did not show any characteristic lines alone oxide.

[0012] 在图2中,紫外吸收结果表面该纳米材料具有极好的吸光性。 [0012] In Figure 2, the results of the surface of the UV absorption of nano-materials have excellent light absorbing.

[0013] 在图3中,透射电镜说明所制备的复合材料在高温焙烧后扔具有均一的尺寸,其粒度在20nm。 [0013] In Figure 3, TEM described composites prepared throw after calcination have a uniform size, having a particle size in 20nm.

[0014] 下面通过实施例对本发明作进一步阐述。 [0014] The following Examples of the present invention will be further described.

具体实施方式 DETAILED DESCRIPTION

[0015]【实施例1】 [0015] [Example 1]

[0016] 高载钛量的纳米Ti02/Zr02复合材料的制备方法。 [0016] The method for preparing a high load capacity of nanometer titanium Ti02 / Zr02 composites. 首先将异丙醇钛和异丙醇锆分散于甲苯中得到混合液I,(甲苯沸点高于水有助于水优先以蒸汽形式扩散到有机溶液表面,水解后的纳米晶体在有机溶剂中收集,有效地避免了毛细凝聚作用导致的纳米结块)。 First, titanium isopropoxide and zirconium isopropoxide dispersed in toluene to obtain mixture I, (toluene having a boiling point higher than water helps the water to preferentially as vapor diffusion surface organic solution, after hydrolysis nanocrystals collected in an organic solvent effectively avoid the effect of capillary condensation caused by agglomeration nanometer). 混合液I的Ti: Zr的摩尔比为1:1 ;其中钛与锆的总摩尔数与有机溶剂的比为0.1: I。 I mixture of Ti: Zr molar ratio is 1: 1; ratio of the total number of moles of titanium and zirconium and wherein the organic solvent is 0.1: I. 在150C条件下,使水蒸气与混合液I相接触,使混合液I中的异丙醇钛和异丙醇锆同时发生水解反应,得到纳米Ti02/Zr02复合材料的前体II。 At 150 C conditions, a mixture of steam and I make contact, I make a mixture of isopropanol and isopropyl titanium zirconium hydrolysis reaction simultaneously to obtain nanometer Ti02 / Zr02 composite precursor II. 空气中干燥后,在600C条件下将前体II焙烧12小时得粒度20纳米左右的Ti02/Zr02复合材料。 After drying in air at 600 C condition II precursor firing 12 hours a particle size of Ti02 / Zr02 composite of 20 nm or so. 产物焙烧前后的XRD粉末衍射谱如图1c所示:X射线谱揭示出Ti02/Zr02复合材料的完美复合。 XRD powder diffraction spectra of the product before and after firing Figure 1c: X-ray spectrum reveals the perfect composite Ti02 / Zr02 composites. 即XRD没有显现出任何单独一种氧化物的特征谱线。 That XRD did not show any characteristic lines alone oxide. 图2为紫外吸收谱透射电镜图,说明制备的纳米晶很好的吸光性。 Figure 2 shows the ultraviolet absorption spectrum of TEM illustrating Nanocrystalline good light absorbing.

[0017]【实施例2〜8】 [0017] [Example 2~8]

[0018] 按照实施例1的方法,只是改变反应温度,有机钛,锆的种类及不同钛锆摩尔比例,可对纳米Ti02/Zr02复合材料进行粒度,Ti: Zr比进一步调节得到不同尺寸,不同载钛量的纳米Ti02/Zr02复合材料。 [0018] The method according to Example 1 except for changing the reaction temperature, organic titanium, zirconium, and different types of titanium-zirconium molar ratio, may Nano Ti02 / Zr02 composite particle size, Ti: Zr ratio further adjusted to get different sizes, different Nano Titanium Content Ti02 / Zr02 composites.

[0019] 具体实施例结果及比较例结果见下表。 [0019] Specific embodiments of results and the results of comparative examples below.

[0020] [0020]

Figure CN103120933AD00051
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Referenced by
Citing PatentFiling datePublication dateApplicantTitle
CN106698509A *17 Nov 201524 May 2017林莉Composite nano zirconium oxide with uniform particle size distribution, and continuous preparation method and equipment thereof
Classifications
International ClassificationB01J21/06, B01J37/00
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