WO2014047937A1 - 一种高热稳定性高活性的钒钛化合物材料及其制备方法 - Google Patents

一种高热稳定性高活性的钒钛化合物材料及其制备方法 Download PDF

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WO2014047937A1
WO2014047937A1 PCT/CN2012/082481 CN2012082481W WO2014047937A1 WO 2014047937 A1 WO2014047937 A1 WO 2014047937A1 CN 2012082481 W CN2012082481 W CN 2012082481W WO 2014047937 A1 WO2014047937 A1 WO 2014047937A1
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vanadium
compound material
titanium compound
titanium
oxide
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PCT/CN2012/082481
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English (en)
French (fr)
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杨祝红
李力成
陆小华
姚文俊
纪拓
李峥
刘畅
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南京工业大学
常熟钰泰隆摩擦材料科技有限公司
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Priority to JP2015533405A priority Critical patent/JP2015533766A/ja
Priority to US14/427,613 priority patent/US9856149B2/en
Priority to PCT/CN2012/082481 priority patent/WO2014047937A1/zh
Publication of WO2014047937A1 publication Critical patent/WO2014047937A1/zh

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Definitions

  • the invention belongs to the technical field of material preparation, and particularly relates to a vanadium titanium compound material with high stability and high activity and a preparation method thereof. Background technique
  • vanadium-titanium compounds have good application in catalytic systems related to environmental protection and energy fields, such as selective catalytic reduction of nitrogen oxides, oxidation of volatile organic compounds, oxidation and oxidation of hydrocarbons, and selective oxidation of hydrocarbons.
  • the catalytic properties of vanadium-titanium compounds are closely related to the structure of titanium oxide, one of which is composed [2] .
  • the natural titanium oxide is divided into three conventional crystal forms: anatase, brookite and rutile, wherein rutile is the stable phase of titanium oxide, and anatase and brookite are metastable phases. In the high temperature heat treatment process, anatase and brookite are finally converted into rutile.
  • the catalytic properties of titanium oxide with different crystal forms after complexing with vanadium oxide are quite different. In general, vanadium-titanium compounds with metastable phase anatase titanium oxide have the best performance.
  • materials often need to face a high temperature environment, which easily leads to crystal transformation of titanium oxide in the vanadium-titanium compound to form rutile-type titanium oxide.
  • Vanadium oxide is easy to form a solid solution with rutile-type titanium oxide, which significantly reduces the catalytic performance of vanadium-titanium compounds [3] .
  • vanadium oxide itself promotes the transformation of titanium oxide, so that the formation temperature of rutile-type titanium oxide in vanadium-titanium compound is lower than that of conventional titanium oxide, which further aggravates the catalytic performance of vanadium-titanium compound [4] .
  • the object of the present invention is to provide a vanadium-titanium compound material which has good thermal stability and catalytic activity in order to solve the above problems, and has a nitrogen oxide removal rate of up to 98% as a catalyst and a volatile organic compound conversion rate of 97% or more. , and no structural additives need to be added during the preparation process.
  • Still another object of the present invention is to provide a method for preparing the vanadium-titanium compound material, which has the advantages of simple process, low cost, and suitability for large-scale industrial production.
  • the object of the present invention can be achieved by the following measures:
  • a high thermal stability and high activity vanadium and titanium compound material is mainly composed of vanadium oxide and titanium oxide, wherein the content of vanadium oxide is 0.5 to 30% of the mass of the vanadium and titanium compound material, in the vanadium and titanium compound material
  • the titanium oxide crystal form is one or a mixture of anatase or Ti0 2 (B).
  • the vanadium-titanium compound material has a vanadium oxide content of 1 to 10% by mass of the vanadium-titanium compound material, and most preferably the vanadium-titanium compound material has a vanadium oxide content of 1 to 5% by mass of the vanadium-titanium compound material.
  • the vanadium-titanium compound material has a specific surface area of from 1 to 200 m 2 /g and a pore volume of from 0.005 to 0.8 cm 3 /g.
  • the vanadium-titanium compound material has a specific surface area of from 1 to 120 m 2 /g, and a pore volume of 0.01 to 0.01 0.4 cm 3 /g.
  • the method for preparing the above-mentioned high thermal stability and high activity vanadium titanium compound material comprises the steps of: adding titanium oxide containing a crystal form of Ti0 2 (B) to a precursor solution containing vanadium, stirring uniformly, and standing still 6 ⁇ After 8 hours, it is dried and then obtained after calcination at 300 to 700 °C.
  • the titanium oxide containing the Ti0 2 (B) crystal form according to the present invention is a titanium oxide having a crystal form of Ti0 2 (B) or a titanium oxide having a total crystal form of Ti 2 2 (B).
  • the titanium oxide of the Ti0 2 (B) crystal form accounts for 1 to 100% by mass of the total titanium oxide, and more preferably, the titanium oxide of the Ti0 2 (B) crystal form accounts for 5 to 100% of the total mass percentage of the titanium oxide. Most preferably, the titanium oxide of the Ti0 2 (B) crystal form accounts for 5% by mass of the total titanium oxide.
  • the titanium oxide containing the Ti0 2 (B) crystal form has a specific surface area of 10 to 300 m 2 /g, a pore volume of 0.02 to 1.0 cm 3 /g, and an average pore diameter of 1.0 to 50 nm.
  • the vanadium-containing precursor is vanadate, vanadyl sulfate or vanadyl oxalate
  • the metavanadate is preferably ammonium metavanadate.
  • the solvent selected for the vanadium-containing precursor solution is water or an organic alcohol, and the organic alcohol is preferably ethanol, and most preferably anhydrous ethanol.
  • the precursor solution containing vanadium preferably has a concentration of 1 to 6 mol/L.
  • the above method may further comprise the steps of: dissolving the vanadium-containing precursor together with a co-solvent in water or an organic alcohol solvent to prepare an immersion liquid, and then adding it to the titanium oxide containing the Ti0 2 (B) crystal form, stirring uniformly, and further It is set for 6 to 8 hours, dried, and then calcined at 300 to 700 ° C to obtain.
  • the ratio of the vanadium-containing precursor solution to the titanium oxide containing the Ti0 2 (B) crystal form is 0.5 to 1.0 mL / g, preferably 0.7 mL / g.
  • titanium oxide has three crystal forms: anatase, rutile, and brookite.
  • Ti0 2 (B) is a new Ti0 2 crystal form discovered late, first discovered by Marchand et al. in 1980.
  • the four crystal structure parameters are shown in Table 1:
  • the shape of titanium oxide in the vanadium-titanium compound material of the present invention is sharp by XRD or Raman spectroscopy. Titanium or one or two of Ti0 2 (B).
  • the preparation of the vanadium-titanium compound material of the present invention does not require the introduction of new structural assistants to improve the thermal stability of titanium oxide in the vanadium-titanium compound material, and the formation temperature of the rutile-type titanium oxide in the vanadium-titanium compound material can be as high as 90 CTC. the above.
  • the vanadium-titanium compound material of the present invention exhibits superior catalytic performance, and as a catalyst, the conversion rate of nitrogen oxides is as high as 98% or more, which is superior to the existing industrial indexes; in addition, the conversion rate of volatile organic compounds is over 97%. .
  • Figure 1 Example of thermal stability investigation. XRD spectrum of a vanadium-titanium compound material.
  • Figure 2 XRD pattern of a vanadium-titanium compound material obtained by a conventional method of thermal stability investigation.
  • the vanadium-titanium compound material prepared according to the present invention does not exhibit a rutile phase, which is pure anatase.
  • the temperature is higher than 90 CTC, gold is present in the sample.
  • the red stone phase; while the vanadium-titanium compound material prepared by the conventional method has a rutile phase after passing through 60 CTC.
  • FIG. 3 TPR spectrum of the vanadium titanium compound material of Example 1 as investigated by thermal stability.
  • Figure 4 TPR spectrum of a vanadium-titanium compound material obtained by a conventional method of thermal stability investigation.
  • the vanadium-titanium compound material prepared according to the present invention has a reduction peak upon treatment at 500 to 1000 °C.
  • the reduction peak intensity of 60CTC was much weaker than that of the 50CTC-treated sample, and the 70CTC-treated sample showed no reduction peak.
  • the crystal form has a specific surface area of 105 m 2 /g, an average pore diameter of 6.2 nm, and a pore volume of 0.23 cm 3 /g.
  • Ammonium metavanadate is used as vanadium-containing precursor
  • oxalic acid is used as a co-solvent
  • the molar ratio of the two is 1:2. It is dissolved in deionized water to prepare a dip solution with a concentration of 0.2 M (ie, a vanadium-containing precursor solution).
  • the impregnation solution was added to the titanium oxide powder containing the Ti0 2 (B) crystal form, and the liquid-solid ratio was 0.7 mL/g (that is, mixed with 0.7 g of titanium oxide having a crystal form of Ti0 2 (B) per mL of the impregnation liquid) Stir well, stand for 8 hours, then dry in an oven, then place in a tube furnace, and roast at 500 °C to obtain vanadium-titanium compound material.
  • Method 1 After cooling, 6 samples were finely ground, and the crystal form of the sample was detected by X-ray powder diffraction (XRD) of the model DSAdlib.
  • the test condition was that the scanning range was between 5 ° and 60 °, and the rate was 0.5 second. /step, set the voltage to 40 kV current to 30 mA, the experimental results are shown in Figure 1.
  • Method 2 After cooling, 6 samples are ground, and the reducing ability of vanadium oxide on the sample is detected by a multi-function adsorption instrument (TPR) model TP-5000. 0.05 g sample is added to the test quartz tube. At 20 ml/min The air velocity is introduced into the air, and the temperature is raised from room temperature to 300 ° C at a rate of 10 ° C / minute for pretreatment, and the temperature is maintained for 0.5 hour. After the temperature is lowered to room temperature, the gas velocity is passed at 20 ml / minute. Into the 20% hydrogen/nitrogen mixture, open the thermal conductivity detector, set the bridge flow to 90 mA, and the thermal conductivity cell temperature to 60 ° C. After the detector is stable, the temperature is taken from the chamber at 10 ° C / min. The temperature was raised to 800 ° C, and the signal was collected by a thermal conductivity detector. The experimental results are shown in Fig. 2.
  • the evaluation device is a quartz tube reactor with an inner diameter of 8 mm; the vanadium-titanium compound material is crushed into particles having a particle size of 1.25 to 3 mm, placed in a constant temperature section of the reactor, and stacked. a length of about 18 cm; the composition of the raw material gas is NO (700 ppm), NH 3 (700ppm), 5 0 2, the remainder being nitrogen; a space velocity of 5000 h- 1, a reaction temperature of 300 ° C.
  • Volatile organic matter removal performance test of vanadium-titanium compound material the performance evaluation is in a fixed-bed microreactor with an inner diameter of 4 mm; a constant temperature section in which a certain amount of vanadium-titanium compound material is added to the reactor; volatile organic compounds
  • toluene the content of toluene in the raw material gas is 1000 ppm, and the rest is air; the reaction temperature is 400 ° C, and the space velocity of the raw material gas is 12,000.
  • the structural parameters and catalytic performance evaluation results of the vanadium-titanium compound material are shown in Table 1.
  • Anatase Ti0 2 , industrial grade K 2 C0 3 (purity 98 wt%), H 2 0 are uniformly mixed, wherein Ti0 2 /K 2 0 molar ratio is 3, water content is 20 wt%; uniformly mixed reaction materials are coated In the alumina pad, the reaction temperature is 1000 ° C, the reaction time is 2 hours, and the sintered product is potassium tetratitanate; the sintered product is crushed and placed in an aqueous solution of HC1 at pH 3 for 24 hours until the solid potassium content is less than the product weight.
  • Vanadium sulphate is used as a vanadium-containing precursor, dissolved in deionized water to prepare an immersion liquid with a concentration of 1 mol/L; the immersion liquid is added to all titanium oxides of Ti0 2 (B) crystal form, and the liquid-solid ratio is 0.7 g/mL (that is, each mL of the impregnation solution is mixed with 0.7 g of titanium oxide which is all Ti0 2 (B) crystal form), stir well, and after standing for 8 hours, it is dried in an oven; then placed in a tube furnace. In the middle, the air is calcined at 600 ° C to obtain a vanadium-titanium compound material.
  • the anatase type titanium oxide was dispersed in a 10 M NaOH aqueous solution at a liquid-solid ratio of 100 mL/g, and then the mixed solution was uniformly stirred, placed in a hydrothermal kettle, and heated to 180 ° C for 48 hours. After cooling to room temperature, the precipitate was collected, immersed in an excess of 0.1 M HCl aqueous solution, and stirred for 24 hours; after completion, the precipitate was washed with deionized water, collected, and dried at 80 °C. The powder is further calcined at 400 °C for 2 hours to obtain titanium oxide powder having a total crystal form of Ti0 2 (B).
  • the crystal form of Ti0 2 (B) has a specific surface area of 50 m 2 /g and a pore volume of 0.15 cm. 3 / g, the average pore size is 12 nm.
  • Adopt Vanadium oxalate is a vanadium-containing precursor, dissolved in deionized water to form an immersion liquid, and the concentration is 0.6 mol/L.
  • the immersion liquid is added to the above titanium oxide, and the liquid solid is as described in Example 1, and the mixture is evenly stirred. After 8 hours, it was placed in an oven for drying; then placed in a tube furnace and fired at 400 ° C to obtain a vanadium-titanium compound material.
  • the double crystal titanium oxide containing the Ti0 2 (B) crystal form and the anatase crystal form prepared according to Example 1 is compared with a commercially available anatase type titanium oxide (commercial titanium oxide type titanium oxide having a specific surface area of 200) m 2 /g, pore volume of 0.35 cm 3 /g, average pore diameter of 5 nm) compounded, the mass ratio of the two is 1: 1, and the obtained crystal form containing Ti0 2 (B) and anatase crystal
  • the content of the Ti0 2 (B) crystal form in the type of double crystal titanium oxide is about 2.5%.
  • Ammonium metavanadate is used as the vanadium-containing precursor, added to absolute ethanol, heated and stirred to prepare an impregnation solution with a concentration of 0.1 mol/L; the amount of the impregnation solution is added to the above titanium oxide, and the liquid-solid ratio is 0.7. mL/g, stir well, let stand for 8 hours, then dry in an oven; then place in a tube furnace and bake at 700 °C. A vanadium titanium compound material is obtained.
  • the titanium oxide prepared by the method of Example 2 was all Ti0 2 (B) crystal form, which was compounded with a commercially available anatase type titanium oxide (the same as in Example 4) at a mass ratio of 1:5. containing Ti0 2 (B) and Form anatase crystal titanium oxide bis Ti0 2 (B) crystalline form content of about 16%.
  • the ammonium metavanadate is used as the vanadium-containing precursor, and the oxalic acid is used as the cosolvent.
  • the molar ratio of the two is 1:2, dissolved in deionized water to form an immersion liquid, the concentration is 3 mol/L;
  • the titanium oxide prepared in accordance with the method of Example 3 was all Ti0 2 (B) crystal form, and was compounded with a commercially available anatase type titanium oxide (same as in Example 4) at a mass ratio of 1:10. containing Ti0 2 (B) and Form anatase crystal titanium oxide bis Ti0 2 (B) crystalline form content of 10%.
  • Vanadium sulphate is used as a vanadium-containing precursor, dissolved in deionized water to form an immersion liquid at a concentration of 2 mol/L.
  • the immersion liquid is added to the above titanium oxide with a content of 10% of Ti0 2 (B).
  • the liquid-solid ratio is 0.7mIJg, and the mixture is evenly stirred. After standing for 8 hours, it is placed in an oven for drying; then placed in a tube furnace and fired at 400 °C. A vanadium titanium compound material is obtained.
  • Example 7 The double crystal titanium oxide containing the Ti0 2 (B) crystal form and the anatase crystal form prepared according to Example 1 is compounded with commercially available amorphous titanium oxide hydrate at a mass ratio of 1:8. containing Ti0 2 (B) and Form anatase crystal titanium oxide bis Ti0 2 (B) crystalline form content of about 1%, a specific surface area of 150 m in the material after firing ° C for 2 hours to obtain 2 /g, pore volume 0.35 cm 3 /g, pore size 8 nm.
  • Vanadium sulphate is used as a vanadium-containing precursor, dissolved in deionized water to form an immersion liquid at a concentration of 6 mol/L.
  • the immersion liquid is added to the above-mentioned Ti0 2 (B) crystal form with an oxidation content of about 1%.
  • the liquid-solid ratio is lm!Jg, and the mixture is evenly stirred. After standing for 8 hours, it is placed in an oven for drying; then placed in a tube furnace and fired at 550 °C. A vanadium titanium compound material is obtained.
  • Tetrabutyl titanate and acetylacetone were slowly added to absolute ethanol at room temperature, and stirred at room temperature for 1 hour; additionally, an ethanol-hydrochloric acid aqueous solution was prepared, which was added to the vigorously stirred titanate at a rate of 1 to 2 drops per second. Stirring in butyl ketone and acetylacetone ethanol solution for 4 h to obtain a transparent and stable sol solution.
  • Ammonium metavanadate is used as the vanadium-containing precursor, dissolved in deionized water to form an immersion liquid, the concentration is 4 mol/L; the immersion liquid is added to the above titanium oxide, the liquid-solid ratio is 0.5 mL/g, stirring After evenly standing for 8 hours, it was dried in an oven, then placed in a tube furnace, and fired at 300 ° C to obtain a vanadium-titanium compound material.
  • Example 2 5 wt% 8 0.02 850 °C 99% 100% anatase
  • Example 3 3 wt% 42 0.13 10.5 Ti0 2 (B) 820 °C 99% 99%
  • Example 6 15 wt% 150 0.28 5.2 700 °C 98% 100% anatase
  • Example 7 30 wt% 50 0.18 8.5 730 ° C 100% 100% anatase
  • Example 8 20 wt% 200 0.45 5.5 anatase 780 ° C 96% 100%
  • the hydrated titanium oxide (Jiangsu Titanium Dioxide Co., Ltd. of Jiangsu province) was used as raw material. After calcination at 500 °C for 2 hours, anatase titanium oxide was obtained with a specific surface area of 150 m 2 /g and a pore volume of 0.3 cm 3 /g. The average pore size is 6.5 nm.
  • the preparation method of the vanadium-titanium compound material is the same as in the first embodiment. According to the material structure and performance evaluation method of Example 1, it was found from the test that the rutile phase appeared when the material was heat-treated at 600 ° C, and the removal rate of nitrogen oxides was 60%.
  • Titanium oxide was prepared by precipitation method according to the literature [7] . 20 mL of tetrabutyl titanate was added to 100 mL of absolute ethanol, and then the mixed solution was added to 100 mL of an aqueous ethanol solution, and the mixed solution was stirred, and the water/tetrabutyl titanate molar ratio was 75. After the white precipitate was formed, stirring was continued for 24 hours, and then the precipitate was collected, and the precipitate was washed with 400 mL of an aqueous ethanol solution.
  • the precipitate was baked in an oven at 80 ° C for 24 hours, and finally the dried powder was heat-treated at 400 ° C for 2 hours to obtain all the anatase type titanium oxide, and the specific surface area of the material was 130. m 2 /g, pore volume 0.25 cm 3 /g, average pore diameter 7 nm. According to the material structure and performance evaluation method of Example 1, it was found from the test that the rutile phase appeared when the material was heat-treated at 500 ° C, and the removal rate of nitrogen oxides was 60%.
  • Example 1 Commercial titanium oxide nanoparticles (Hangzhou Wanjing New Material Co., Ltd.); specific surface area of 88.3 m 2 /g, pore volume of 0.05 cm 3 /g, particle size of about 10 nm. According to the material structure and performance evaluation method of Example 1, it was found from the test that the rutile phase appeared when the material was heat-treated at 550 ° C, and the removal rate of nitrogen oxides was 68%.
  • the vanadium-titanium compound material reported in [8] wherein the titanium oxide crystal form is anatase, and 9 wt% of tungsten oxide is added as a structural auxiliary agent to improve the thermal stability of the vanadium-titanium compound material.
  • the rutile formation temperature of this compound was 600 ° C, and the conversion of nitrogen oxides was 95%.

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Abstract

本发明公开了一种高热稳定性高活性的钒钛化合物材料及其制备方法。所述钒钛化合物材料主要是由氧化钒和氧化钛复合而成，其中，氧化钒的含量为钒钛化合物材料质量的0.5～30%，钒钛化合物材料中的氧化钛晶型为锐钛矿或者TiO2(B)中的一种或者两种混合。与现有技术相比，本发明钒钛化合物材料无需添加任何结构助剂，兼具良好的热稳定性和催化活性，金红石型氧化钛的生成温度可高达900℃以上。另外，本发明材料制备方法简单，成本低，适合工业化大生产。

Description

一种高热稳定性高活性的钒钛化合物材料及其制备方法
技术领域
本发明属于材料制备技术领域， 具体涉及一种高稳定性高活性的钒钛化合物材料及其 制备方法。 背景技术
据统计， 从 1967〜2000年间， 关于过渡金属催化应用公开发表的论文， 其中 28%与钒 有关， 15%与钛有关，大量的报道表明钒和钛在众多催化反应体系中一直受到人们的广泛关 注[1]。 特别是钒钛化合物， 较其他材料在氮氧化物的选择性催化还原、 挥发性有机物氧化、 硫化氢氧化、 烃类的选择性氧化等与环保、 能源领域有关的催化体系中具有良好的应用前 钒钛化合物的催化性能与其组成之一的氧化钛的结构密切相关 [2]。自然界中的氧化钛分 三种常规晶型： 锐钛矿、 板钛矿和金红石， 其中金红石为氧化钛的稳相， 锐钛矿和板钛矿 为介稳相。 在高温热处理过程中， 锐钛矿和板钛矿最终转变成金红石。 不同晶型的氧化钛 与氧化钒复合后的催化性能差别较大。 一般情况下， 以介稳相锐钛矿型氧化钛的钒钛化合 物性能最佳。 但是， 在材料的制备或者应用过程中， 材料往往需要面临高温环境， 这容易 导致钒钛化合物中的氧化钛出现转晶现象， 生成金红石型氧化钛。 而氧化钒易与金红石型 氧化钛形成固溶体， 显著降低钒钛化合物的催化性能 [3]。 另外， 氧化钒本身也会促进氧化钛 发生转晶， 以致钒钛化合物中金红石型氧化钛的生成温度低于常规的氧化钛， 进一步加剧 钒钛化合物催化性能的下降 [4]。
目前， 大量的工作集中在如何解决钒钛化合物的稳定性差以保持其高性能的问题上。 普遍的做法是引入结构助剂（钨、钼、铝、硅、钾等）来提高金红石型氧化钛的生成温度 [5]。 结构助剂的添加虽然在一定程度上可以缓解锐钛矿型氧化钛转成金红石型氧化钛， 但是也 存在一系列的问题。 例如， 一些结构助剂对于氧化钒的分散状态影响较大， 这容易造成钒 钛化合物的催化性能大幅度下降； 另外， 例如在用于脱硝反应中的钒钛化合物， 氧化钨或 者氧化钼作为结构助剂， 其使用量达到往往是化合物中氧化钒用量的 8〜10倍， 这导致钒 钛化合物的成本显著提升 [6]。因此， 如何能够提高钒钛化合物稳定性的同时又保持其良好的 注能， 仍然是业界关注的焦点。 发明内容
本发明的目的是为了解决上述问题提供一种钒钛化合物材料， 该材料兼具良好的热稳 定性和催化活性， 作为催化剂氮氧化物脱除率高达 98%， 挥发性有机物转化率 97%以上， 且制备过程中无需添加任何结构助剂。
本发明的又一个目的是提供该钒钛化合物材料的制备方法， 该方法具有过程简单， 成 本较低， 适合大规模工业化生产等优点。
本发明目的可以通过以下措施达到：
一种高热稳定性高活性的钒钛化合物材料， 该材料主要是由氧化钒和氧化钛复合而成， 其中， 氧化钒的含量为钒钛化合物材料质量的 0.5〜30%， 钒钛化合物材料中的氧化钛晶型 为锐钛矿或者 Ti02(B)中的一种或者两种混合。优选钒钛化合物材料中氧化钒的含量为钒钛 化合物材料质量的 1〜10%，最优选钒钛化合物材料中氧化钒的含量为钒钛化合物材料质量 的 1〜5%。
上述钒钛化合物材料的比表面积为 l〜200 m2/g， 孔容为 0.005〜0.8 cm3/g， 优选钒钛化 合物材料的比表面积为 l〜120 m2/g， 孔容为 0.01〜0.4cm3/g。
上述高热稳定性高活性的钒钛化合物材料的制备方法， 该方法包括以下步骤： 将含有 Ti02(B)晶型的氧化钛加入到含有钒的前驱体溶液中， 搅拌均匀， 静置 6〜8小时， 烘干， 再 在 300〜700°C条件下焙烧后获得。本发明所述的含有 Ti02(B)晶型的氧化钛为一部份晶型为 Ti02(B)的氧化钛或全部晶型为 Ti02(B)的氧化钛。 优选 Ti02(B)晶型的氧化钛占全部氧化钛 质量百分含量 1〜100%， 进一步优选 Ti02(B)晶型的氧化钛占全部氧化钛质量百分含量的 5〜100%， 最优选 Ti02(B)晶型的氧化钛占全部氧化钛质量百分含量 5%。
上述含有 Ti02(B)晶型的氧化钛的比表面积为 10〜300 m2/g， 孔容为 0.02〜1.0 cm3/g, 平均孔径为 1.0〜50nm。本发明选用含钒的前驱体为偏钒酸盐、硫酸氧钒或者草酸氧钒， 所 述的偏钒酸盐优选偏钒酸铵。 含有钒的前驱体溶液选用的溶剂为水或者有机醇， 所述的有 机醇以乙醇为佳， 最佳为无水乙醇。 含有钒的前驱体溶液优选浓度为 l〜6mol/L。
上述方法还可以包括以下步骤： 将含有钒的前驱体与助溶剂一同溶解在水或者有机醇 溶剂中制成浸渍液， 再加入到含有 Ti02(B)晶型的氧化钛中搅拌均匀， 静置 6〜8小时， 烘 干， 再在 300〜700°C条件下焙烧后获得。含有钒的前驱体溶液与含有 Ti02(B)晶型的氧化钛 的用量比为 0.5〜1.0 mL /g， 优选为 0.7 mL/g。 通常氧化钛有三种晶型：锐钛矿（anatase)、金红石（rutile)和板钛矿（brookite)。 Ti02(B) 是较晚发现的一种新的 Ti02晶型， 由 Marchand等人于 1980年首次发现， 四种晶型结构参 数如表 1 :
表 1 1102晶型的结构参数
iS又
晶型 空间群 晶胞参数 （nm) 文献来源
(g-cm- 3) 金红石 4.13 a = 0.459, c = 0.296
m
锐钛 I4j/amd 3.79 a = 0.379, c = 0.951
板钛 Pbca 3.99 a = 0.917， 6 = 0.546， c = 0.514
Ti02(B) I4/m 3.64 a = 1.216， 6 = 0.374， c = 0.651 , = 107.3° Marchand (1980) 利用 XRD 或者拉曼光谱检测， 本发明钒钛化合物材料中的氧化钛晶型为锐钛矿或者 Ti02(B)中的一种或者两种。
与现有技术比较本发明的有益效果：
( 1 ) 本发明的钒钛化合物材料的制备过程中无需引入新的结构助剂来提高钒钛化合 物材料中氧化钛的热稳定性，钒钛化合物材料中金红石型氧化钛的生成温度可高达 90CTC以 上。
(2) 本发明的钒钛化合物材料表现优越的催化性能， 作为催化剂， 其氮氧化物的转 化率高达 98%以上， 优于现有工业指标； 另外， 挥发性有机物的转化率达到 97%以上。
(3) 本发明的钒钛化合物材料的制备方法过程简单， 成本较低， 适合大规模工业化 生产。 附图说明
图 1 : 经过热稳定性考察的实施例 1钒钛化合物材料的 XRD谱图。
图 2: 经过热稳定性考察的常规方法获得钒钛化合物材料的 XRD谱图。
由图 1-2所示， 经过 500〜800°C热处理测试， 根据本发明制备的钒钛化合物材料没有 显示出金红石相， 为纯锐钛矿， 当温度高于 90CTC时， 样品中才出现金红石相； 而常规方法 制备的钒钛化合物材料在经过 60CTC时， 便出现金红石相。
图 3: 经过热稳定性考察的实施例 1钒钛化合物材料的 TPR谱图。 图 4: 经过热稳定性考察的常规方法获得钒钛化合物材料的 TPR谱图。 由图 3-4所示， 根据本发明制备的钒钛化合物材料在经过 500〜1000°C处理， 均出现还 原峰。 而根据常规方法制备的钒钛化合物材料， 60CTC的还原峰强度已比 50CTC处理的样品 减弱非常多， 而 70CTC处理的样品没有出现还原峰。这些差别表明本发明方法制备的钒钛化 合物材料具有优良的热稳定性。 具体实施方式
下面根据实施例对本发明作进一步描述， 以下实施例的具体实施方案只是更具体地说 明本发明， 本发明并不限于以下实施例的内容。
实施例 1 :
根据专利 （ZL0315827.5 )所述的方法将锐钛型氧化钛， 工业级 K2C03 (纯度 98wt%)， H20均匀混合， 其中 Ti02/K20摩尔比为 1.9， 含水量 20wt% ; 将混合好的反应物料均匀涂 于氧化铝垫板， 反应温度 880 °C， 反应时间为 2小时， 烧结产物为二钛酸钾； 烧结产物在 水中分散后， 置于 50 °C、 5倍的 pH=8的水溶液中反应 8小时， 过滤后置于 pH为 3的盐酸 水溶液搅拌 8小时， 至固含钾量小于产物重量的 0.5wt% ; 水洗， 过滤， 20〜50 °C干燥 12 小时得到水合产物； 在 500 °C空气中晶化 2小时， 得到含有 Ti02(B)晶型的氧化钛， 该氧化 钛含有 95%的锐钛矿晶型和 5%的 Ti02(B)晶型， 比表面积为 105 m2/g， 平均孔径为 6.2 nm， 孔容为 0.23 cm3/g。 采用偏钒酸铵为含钒的前躯体， 草酸为助溶剂， 两者的摩尔比为 1 :2， 溶解于去离子水中配成浓度为 0.2 M的浸渍液 （即含有钒的前驱体溶液）； 将浸渍液加入到 含有 Ti02(B)晶型的氧化钛粉末中，液固比为 0.7 mL/g(即每 mL浸渍液与 0.7 g全部为 Ti02(B) 晶形的氧化钛混合）， 搅拌均匀， 静置 8小时后， 置于烘箱中烘干， 然后再置于管式炉中， 通空气 500 °C焙烧， 获得钒钛化合物材料。
钒钛化合物材料的热稳定性测试:将钒钛化合物材料置于马弗炉中，分别经过 500， 600， 700， 800， 900和 100CTC六个温度焙烧， 时间分别为 2小时。
方法一：待冷却后，将 6个样品研细，通过型号为 DSAdavance的 X射线粉末衍射（XRD ) 检测样品的晶型， 测试条件为扫描范围在 5 ° 〜60° 之间， 速率为 0.5秒 /步， 设置电压为 40千伏电流为 30毫安， 实验结果见图 1。
方法二： 待冷却后， 将 6个样品研细， 通过型号为 TP-5000的多功能吸附仪（TPR)检 测样品上氧化钒的还原能力， 称取 0.05克样品加入到测试石英管中， 先以 20毫升 /分钟的 气速通入空气， 以 10°C/分钟的速度将温度从室温升至 300°C进行预处理， 保温 0.5小时； 结束后待温度降至室温后， 以 20毫升 /分钟的气速通入 20%氢气 /氮气混合气， 打开热导检 测器， 桥流设置为 90毫安， 热导池温度为 60°C ; 待检测器稳定后， 以 10°C/分钟的速度将 温度从室温升至 800°C， 并通过热导检测器采集信号， 实验结果见图 2。
钒钛化合物材料的氮氧化物脱除性能测试： 评价装置为内径 8mm的石英管反应器； 将 钒钛化合物材料压片破碎至粒度为 1.25~3 mm的颗粒， 置于反应器恒温段， 堆积长度为 18 cm左右； 原料气的组成为 NO ( 700 ppm)、 NH3 (700ppm)、 5 02, 其余为氮气； 空速为 5000 h-1 , 反应温度为 300°C。
钒钛化合物材料的挥发性有机物脱除性能测试：该性能评价是在内径为 4 mm的固定床 微型反应器； 称取一定量的钒钛化合物材料加入到反应器中的恒温段； 挥发性有机物为甲 苯，原料气中甲苯的含量为 1000 ppm，其余为空气；反应温度为 400 °C，原料气空速为 12000 钒钛化合物材料的各项结构参数和催化性能评价结果如表 1所示。
实施例 2:
将锐钛型 Ti02， 工业级 K2C03 (纯度 98wt% )， H20均匀混合， 其中 Ti02/K20摩尔比 为 3， 含水量 20wt% ; 将混合好的反应物料均匀涂于氧化铝垫板， 反应温度 1000 °C， 反应 时间为 2小时， 烧结产物为四钛酸钾； 烧结产物破碎， 置于 pH为 3的 HC1水溶液搅拌 24 小时， 至固含钾量小于产物重量的 0.5wt% ; 水洗， 过滤， 20〜50 °C干燥 12小时得到水合 产物;在 400 °C空气中晶化 2小时，得到全部为 Ti02(B) 晶形的氧化钛，比表面积为 20 m2/g， 孔容为 0.03 cm3/g。 采用硫酸氧钒为含钒的前躯体， 溶解于去离子水中配成浓度为 1 mol/L 的浸渍液； 将浸渍液加入到全部为 Ti02(B) 晶形的氧化钛中， 液固比为 0.7 g/mL (即每 mL 浸渍液与 0.7 g全部为 Ti02(B) 晶形的氧化钛混合）， 搅拌均匀， 静置 8小时后， 置于烘箱 中烘干； 然后再置于管式炉中， 通空气 600 °C焙烧， 获得钒钛化合物材料。
钒钛化合物材料的各项结构参数和催化性能评价结果如表 1所示。
实施例 3:
将锐钛矿型氧化钛分散于 lO M NaOH水溶液中， 液固比为 lOO mL/g, 然后将混合溶液 搅拌均匀， 置于水热釜中， 加热至 180 °C保温 48小时。 待冷却至室温后， 收集沉淀物， 浸 入到过量的 0.1 M HC1水溶液中， 搅拌 24小时； 结束后， 用去离子水洗涤沉淀物， 收集， 在 80 °C条件下烘干。粉末再经 400 °C焙烧 2小时，得到全部晶型为 Ti02(B)的氧化钛粉末， 晶型为 Ti02(B)的氧化钛比表面积为 50 m2/g， 孔容为 0.15 cm3/g, 平均孔径为 12 nm。 采用 草酸氧钒为含钒的前躯体， 溶解于去离子水中配成浸渍液， 浓度为 0.6 mol/L; 量取浸渍液 加入到上述氧化钛中， 液固比如实例 1所述， 搅拌均匀， 静置 8小时后， 置于烘箱中烘干; 然后再置于管式炉中， 通空气 400 °C焙烧， 获得钒钛化合物材料。
钒钛化合物材料的各项结构参数和催化性能评价结果如表 1所示。
实施例 4:
根据实施例 1制备得到的含有 Ti02(B)晶型和锐钛矿晶型的双晶氧化钛， 将其与市售锐 钛矿型氧化钛（市售钛矿型氧化钛比表面积为 200 m2/g，孔容为 0.35 cm3/g,平均孔径为 5 nm) 进行复配， 两者的质量比为 1 : 1，， 获得的含有 Ti02(B)晶型和锐钛矿晶型双晶氧化钛中 Ti02(B)晶型的含量为 2.5%左右。 采用偏钒酸铵为含钒的前躯体， 加入到无水乙醇中， 加热 搅拌，配成浓度为 0.1 mol/L的浸渍液；量取浸渍液加入到上述氧化钛中，液固比为 0.7 mL/g, 搅拌均匀， 静置 8小时后， 置于烘箱中烘干； 然后再置于管式炉中， 通空气 700 °C焙烧。 获得钒钛化合物材料。
钒钛化合物材料的各项结构参数和催化性能评价结果如表 1所示。
实施例 5:
根据实施例 2方法制备得到的全部为 Ti02(B) 晶形的氧化钛， 将其与市售锐钛矿型氧 化钛 （同实施例 4)进行复配， 质量比为 1 : 5， 获得的含有 Ti02(B)晶型和锐钛矿晶型双晶 氧化钛中 Ti02(B)晶型的含量为 16%左右。 采用偏钒酸铵为含钒的前躯体， 草酸为助溶剂， 两者的摩尔比为 1:2， 溶于去离子水中配成浸渍液， 浓度为 3 mol/L; 量取浸渍液， 加入到 上述 Ti02(B)晶型的含量为 16%左右的氧化钛中， 液固比为 0.7 mIJg， 搅拌均匀， 静置 8小 时后， 置于烘箱中烘干； 然后再置于管式炉中， 通空气 50CTC焙烧。 获得钒钛化合物材料。
钒钛化合物材料的各项结构参数和催化性能评价结果如表 1所示。
实施例 6:
根据实施例 3方法制备得到的全部为 Ti02(B) 晶形的氧化钛， 将其与市售锐钛矿型氧 化钛 （同实施例 4) 进行复配， 质量比为 1 : 10， 获得的含有 Ti02(B)晶型和锐钛矿晶型双 晶氧化钛中 Ti02(B)晶型的含量为 10%。 采用硫酸氧钒为含钒的前躯体， 溶于去离子水中配 成浸渍液， 浓度为 2 mol/L; 量取浸渍液加入到上述 Ti02(B)晶型的含量为 10%的氧化钛中， 液固比为 0.7mIJg， 搅拌均匀， 静置 8小时后， 置于烘箱中烘干； 然后再置于管式炉中， 通 空气 400 °C焙烧。 获得钒钛化合物材料。
钒钛化合物材料的各项结构参数和催化性能评价结果如表 1所示。
实施例 7: 根据实施例 1制备得到的含有 Ti02(B)晶型和锐钛矿晶型的双晶氧化钛， 将其与市售无 定形水合氧化钛进行复配， 质量比为 1 : 8， 经 500 °C焙烧 2小时后， 获得的含有 Ti02(B) 晶型和锐钛矿晶型双晶氧化钛中 Ti02(B)晶型的含量为 1%左右， 材料的比表面积为 150 m2/g， 孔容为 0.35 cm3/g， 孔径为 8 nm。 采用硫酸氧钒为含钒的前躯体， 溶于去离子水中配 成浸渍液， 浓度为 6 mol/L; 量取浸渍液加入到上述 Ti02(B)晶型的含量为 1%左右的氧化钛 中， 液固比为 lm!Jg, 搅拌均匀， 静置 8小时后， 置于烘箱中烘干； 然后再置于管式炉中， 通空气 550 °C焙烧。 获得钒钛化合物材料。
实施例 8:
将钛酸四丁酯和乙酰丙酮同时缓慢加入到无水乙醇中， 在室温下搅拌 l h; 另外配制乙 醇-盐酸水溶液， 将其以每秒 1~2滴的速度加入到剧烈搅拌的钛酸四丁酯和乙酰丙酮乙醇溶 液中， 继续搅拌 4 h， 得到透明稳定的溶胶液， 各物质的摩尔比为 Ti: 无水乙醇： 水： 乙酰 丙酮 =1:20:5:0.3; 待样品凝胶后， 再在室温条件下陈化 2天， 制成的溶胶。
然后根据实施例 2方法制备得到的全部晶形为 Ti02(B)的氧化钛投入上述溶胶中， 质量 比为 1 : 20， 搅拌 6 h， 置于烘箱中烘干； 400 °C焙烧 2 h， 制得全部为 Ti02(B)晶型的氧化 钛。 采用偏钒酸铵为含钒的前躯体， 溶于去离子水中配成浸渍液， 浓度为 4 mol/L; 量取浸 渍液加入到上述氧化钛中， 液固比为 0.5 mL/g， 搅拌均匀， 静置 8小时后， 置于烘箱中烘 干， 然后再置于管式炉中， 通空气 300 °C焙烧.获得钒钛化合物材料。
氧化钒 结构参数
挥发性有 的质量 氮氧化物 比表面积 平 晶型组成 机物转化 百分含 转化率
m /g cm /g nm
实施例 1 1 wt% 98 0.23 6 锐钛矿 900 °C 98% 97%
Ti02(B) +
实施例 2 5 wt% 8 0.02 850 °C 99% 100% 锐钛矿 实施例 3 3 wt% 42 0.13 10.5 Ti02(B) 820 °C 99% 99%
实施例 4 0.5 wt% 1 0.01 锐钛矿 850 °C 85% 88%
实施例 5 10 wt% 120 0.32 6.3 锐钛矿 800 °C 98% 98%
Ti02(B) +
实施例 6 15 wt% 150 0.28 5.2 700 °C 98% 100% 锐钛矿
Ti02(B) +
实施例 7 30 wt% 50 0.18 8.5 730 °C 100% 100% 锐钛矿 实施例 8 20 wt% 200 0.45 5.5 锐钛矿 780 °C 96% 100%
比较例 1 :
以水合氧化钛 （江苏省镇江钛白粉股份有限公司） 为原料， 经过 500 °C焙烧 2小时后 得到锐钛矿型氧化钛， 比表面积为 150 m2/g， 孔容为 0.3 cm3/g， 平均孔径为 6.5 nm。 以此 为钒钛化合物材料的基材， 钒钛化合物材料的制备方法与实施例 1 中相同。 根据实施例 1 的材料结构与性能评价方法， 由试验可知， 材料经 600 °C热处理便出现金红石相， 氮氧化 物的脱除率为 60%。
比较例 2:
根据文献[7]报道沉淀法制备氧化钛。量取 20 mL钛酸四丁酯加入到 100 mL的无水乙醇 中， 接着将该混合溶液加入到 100 mL乙醇水溶液中， 搅拌混合溶液， 水 /钛酸四丁酯的摩 尔比为 75。 待形成白色沉淀物后， 继续搅拌 24小时， 然后收集沉淀物， 用 400 mL乙醇水 溶液洗涤沉淀物。 洗涤结束后， 将沉淀物置于 80 °C烘箱中烘 24小时， 最终将干燥的粉末 经 400 °C热处理 2小时后，获得全部晶型为锐钛矿型氧化钛，该材料的比表面积为 130 m2/g， 孔容为 0.25 cm3/g , 平均孔径为 7 nm。根据实施例 1的材料结构与性能评价方法， 由试验可 知， 材料经 500 °C热处理便出现金红石相， 氮氧化物的脱除率为 60%。
比较例 3 :
商业氧化钛纳米颗粒（杭州万景新材料有限公司）； 比表面积为 88.3 m2/g， 孔容为 0.05 cm3/g , 颗粒大小约为 10 nm。 根据实施例 1的材料结构与性能评价方法， 由试验可知， 材 料经 550 °C热处理便出现金红石相， 氮氧化物的脱除率为 68%。
比较例 4:
文献 [8]报道的钒钛化合物材料， 其中的氧化钛晶型为锐钛矿， 化合物中添加了 9wt% 氧化钨作为结构助剂以提高钒钛化合物材料的热稳定性。该化合物的金红石生成温度为 600 °C， 氮氧化物的转化率为 95%。
比较例 5 :
根据文献报道 [9]的改进方法， 添加 5wt%含量的二氧化硅作为结构助剂以提高钒钛化合 物材料的热稳定性。 该化合物的金红石生成温度为 730 °C， 而氮氧化物的转化率仅为 30%， 挥发性有机物的脱除率为 45%。 参考资料：
[1] Weckhuysen BM, Keller DE (2003) Catalysis Today 78:25
[2] Wachs IE, Weckhuysen BM (1997) Appl Catal A Gen 157:67
[3] Saleh RY, Wachs IE, Chan SS, Chersich CC (1986) Journal of Catalysis 98:102
[4] Banares MA, Alemany L, amp, x, s J, Jimenez MC, Larrubia MA, Delgado F, Granados ML, Marti, nez-Arias A, Blasco JM, Fierro JL， s G (1996) Journal of Solid State Chemistry 124:69 [5] Reddy BM, Ganesh I, Chowdhury B (1999) Catalysis Today 49:115
[6] Madia G, Elsener M, Koebel M, Raimondi F, Wokaun A (2002) Applied Catalysis B:
Environmental 39:181
[7] Zhang J, Li M, Feng Z， Chen J, Li C (2006) Journal of Physical Chemistry B 110:927
[8] Djerad S, Tifouti L, Crocoll M, Weisweiler W (2004) Journal of Molecular Catalysis A:
Chemical 208:257
[9] Okada K, Yamamoto N, Kameshima Y, Yasumori A, MacKenzie KJD (2001) Journal of the American Ceramic Society 84:1591
_ io _

Claims

权利要求书
1. 一种高热稳定性高活性的钒钛化合物材料，其特征在于所述钒钛化合物材料主要是由氧化 钒和氧化钛复合而成， 其中， 氧化钒的含量为钒钛化合物材料质量的 0.5〜30%， 钒钛化 合物材料中的氧化钛晶型为锐钛矿或者 Ti02(B)中的一种或者两种混合。
2. 根据权利要求 1所述的高热稳定性高活性的钒钛化合物材料，其特征在于所述钒钛化合物 材料中氧化钒的含量为钒钛化合物材料质量的 1〜10%。
3. 根据权利要求 1所述的高热稳定性高活性的钒钛化合物材料，其特征在于所述钒钛化合物 材料中氧化钒的含量为钒钛化合物材料质量的 1〜5%。
4. 一种高热稳定性高活性的钒钛化合物材料，其特征在于所述的钒钛化合物材料的比表面积 为 l〜200m2/g， 孔容为 0.005〜0.8cm3/g。
5. 一种高热稳定性高活性的钒钛化合物材料的制备方法， 其特征在于该方法包括以下步骤： 将含有 Ti02(B)晶型的氧化钛加入到含有钒的前驱体溶液中， 搅拌均匀， 静置 6〜8小时， 烘干， 再在 300〜700°C条件下焙烧后获得。
6. 根据权利要求 5所述的钒钛化合物材料的制备方法， 其特征在于含有 Ti02(B)晶型的氧化 钛中， 晶型为 Ti02(B)的氧化钛的含量为 1〜100%。
7. 根据权利要求 6所述的钒钛化合物材料的制备方法， 其特征在于含有 Ti02(B)晶型的氧化 钛中， 晶型为 Ti02(B)的氧化钛的含量为 5〜100%。
8. 根据权利要求 5所述的钒钛化合物材料的制备方法， 其特征在于选用的含有 Ti02(B)晶型 的氧化钛的比表面积为 10〜300 m2/g， 孔容为 0.02〜1.0 cm3/g， 平均孔径为 1.0〜50 nm。
9. 根据权利要求 5 所述的钒钛化合物材料的制备方法， 其特征在于含钒的前驱体为偏钒酸 盐、 硫酸氧钒或者草酸氧钒， 含有钒的前驱体溶液选用的溶剂为水或者有机醇。
10.根据权利要求 9所述的钒钛化合物材料的制备方法， 其特征在于所述的有机醇为乙醇。
11.根据权利要求 5所述的钒钛化合物材料的制备方法，其特征在于所述的含有钒的前驱体溶 液的浓度为 l〜6mol/L。
12.根据权利要求 5所述的钒钛化合物材料的制备方法，其特征在于所述的含有钒的前驱体溶 液与含有 Ti02(B) 晶型的的氧化钛的用量比为 0.5〜1.0 mL /g 。
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