不同酸处理钛酸锂的转型研究

详细研究了酸的种类和处理时间对钛酸锂转型的影响. 结果显示当相同酸度的硫酸和盐酸用来对钛酸锂进行改性时,在盐酸介质中钛酸锂更容易转变为锐钛矿和金红石型二氧化钛. 硫酸浓度越高,钛酸锂更容易转变为锐钛矿和金红石型二氧化钛;处理时间越长,更多的钛酸锂可以转变为锐钛矿和金红石型二氧化钛. 硫酸根通过螯合双齿配位于二氧化钛,有利于稳定锐钛矿型晶相;亲电的H+和高电负性的Cl-影响Ti-O键,导致TiO6八面体中的Ti-O键断裂和锐钛矿型二氧化钛发生结构重排形成金红石型二氧化钛. 钛锂离子筛稳定的结构和晶相组成能够保证高效、循环往复地提取锂,从这一点来看,相比于盐酸,硫酸更适合作为洗脱剂来制备钛锂离子筛,并且低浓度的盐酸是更好的选择.     

硫酸氧钛水解影响因素的研究

以硫酸法钛白工业生产的水解工艺为基础 ,提出了一个影响水解产物偏钛酸粒度及其分布的新因素———加热延迟时间 .通过正交试验和极差分析探讨了F(mH2 SO4 /mTiO2 )值、铁钛比 (mFe/mTiO2 )、水解液初始钛浓度等因素 ,尤其是加热延迟时间 ,对水解产物偏钛酸粒度的影响 .在水解 1h和 2h后 ,各因素对偏钛酸粒度大小的影响从大到小的顺序分别是 :铁钛比、水解液初始钛浓度、F值、加热延迟时间、熟化时间 ;水解液初始钛浓度、铁钛比、F值、熟化时间、加热延迟时间 .对偏钛酸粒度分布影响最大的两个因素为水解液初始钛浓度和加热延迟时间 .在粒度分布比较集中的条件下得到了水解的最优化条件 :水解液初始钛浓度 ,1 95mol/L ;F值 ,2 10 ;铁钛质量比 ,0 4 ;加热延迟时间 ,10min ;熟化时间 ,30min .     

纳米级TiO_2超细粉的水热合成及结构相变的研究

利用水热合成法以无水ＴｉＣｌ４和浓硫酸为原料制备了纳米级锐钛矿型ＴｉＯ２超细粉，并对其由锐钛型到金红石型结构的转变温度进行了研究，结果显示，其相变温度比传统的ＴｉＯ２材料要低得多。     

Al掺杂TiO_2的制备及酸化处理对其光催化活性的影响

锐钛矿相TiO2的光催化活性高于金红石相。采用化学溶液分解法制备了Al掺杂锐钛矿TiO2,并用硝酸对其进行酸化处理。利用TG-DTA、XRD、FTIR、BET和UV-vis等手段对样品进行了表征,通过对甲基橙的降解分析了酸化处理对Al掺杂TiO2光催化活性的影响。结果表明:掺杂Al能有效抑制TiO2由锐钛矿向金红石转变。酸化处理因能增大Al掺杂TiO2的比表面积而使其光催化活性提高。Al/Ti掺杂比为1∶4的样品在酸化处理后具有的光催化活性最高,60min后对甲基橙的降解达到100%。     

Influence of catalyst on structural and morphological properties of TiO2 nanostructured films prepared by sol–gel on glass

Transparent TiO2 thin films have been prepared by the sol-gel method using titanium alkoxides as precursors.Thin films were deposited on glass supports by the dip-coating technique.The TiO2 layer acts as a self-cleaning coating generated from its photocatalysis and photoinduced superhydrophilicity.The crystalline structure of TiO2 films was dominantly identified as the anatase phase,consisted of uniform spherical particles of about 14-50 nm in size,which strongly depends upon catalyst-type and heat treatment temperature.Increasing heat treating temperature can lead to an increase in crystalline size.The results indicated that the sample S.S(sample derived from sol containing sulfuric acid as catalyst) exhibits superhydrophilic nature and better photocatalytic activity,which can be attributed to its higher anatase content and lower crystalline size.Morphological studies,carried out using Atomic Force Microscopy(AFM),confirm the presence of crystalline phase with such a grain size and low surface roughness.Thus,the applied films exhibiting high photocatalytic activity,superhydrophilic behavior,and low surface roughness can be used as an efficient self-cleaning coating on glass and other optical applications.     

自由基抑制剂对不同晶型TiO2光催化反应的影响

以荧光光谱法研究了不同晶型 TiO₂ 的光催化反应体系中羟基自由基(·OH)的产生情况,表明在H₂O₂存在条件下,金红石型 TiO₂ 经可见光激发可持续稳定产生·OH,而以锐钛矿型 TiO₂ 作光催化剂时,则检测不到·OH的生成。光催化结果表明,在H₂O₂存在条件下,苯酚可被 TiO₂ 可见光催化降解;往反应体系加入自由基抑制剂(叔丁醇或甲醇)时,明显降低了金红石型 TiO₂ 的降解效率,但对锐钛矿型 TiO₂ 的影响较弱。以金红石型 TiO₂ 作光催化剂时,苯酚的降解反应主要发生在溶液中;而以锐钛矿型 TiO₂ 作光催化剂时,则苯酚的降解反应主要发生在催化剂的表面。     

水热法可控合成的高径向比金红石型纳米TiO_2颗粒

以异丙醇钛为原料,采用水热法在浓酸条件下低温合成高径向比金红石型TiO2纳米颗粒.研究了酸浓度、聚乙二醇4000(PEG4000)、十六烷基溴化铵(CTAB)和十二烷基硫酸钠(SDS)对产物形貌和大小的影响.首次采用Zeta电位仪测试了金红石型和锐钛矿型纳米TiO2颗粒对H+的吸附能力,从而揭示了金红石型纳米TiO2颗粒呈针状的原因.经透射电镜(TEM)和X射线衍射(XRD)分析,得到的样品为金红石型,其颗粒为棒状,通过控制条件可以制得不同粒径分散均匀的纳米TiO2颗粒.     

Extraction behaviours of titanium and other impurities in the decomposition process of ilmenite by highly concentrated KOH solution

To effectively utilize ilmenite and recycle KOH solution, the extraction behaviours of titanium and other associated impurities in the decomposition process of ilmenite by highly concentrated KOH solution were studied. Experiments on the extraction behaviours of titanium as well as other associated impurities of ilmenite such as iron, silicon, calcium, and aluminium were carried out. The effects of various parameters, including reaction temperature, KOH concentration, reaction time, alkali-to-ore mass ratio, and particle size on the extraction rate of titanium and other impurities were examined. When the finely ground ore (58-75 μm) reacted with KOH solution (80wt%) in an alkali-to-ore mass ratio of 7:1 at 260℃ for 60 min, almost complete extraction of titanium was achieved, while the extraction rate of aluminium was 78% and that of other impurities was less than 22%. Moreover, high purity (98.2wt%) TiO₂ with the anatase structure could be gained in the purification process.     

处理频率对TC4钛合金微弧氧化膜特性的影响

利用自制多功能微弧氧化膜的制备系统对TC4钛合金进行表面处理, 通过扫描电镜(SEM)和X射线衍射仪(XRD)研究脉冲频率(f)对氧化膜生长特性、 表面形貌和相组成的影响. 结果表明, 当f≤2 000 Hz时, 成膜速率随f增加迅速减小; 当2 000 Hz＜f＜4 000 Hz时, 成膜速率随f增加而减小的趋势变缓; 当f≥4 000 Hz时, 成膜速率不随f发生变化. 该氧化膜表面多孔, 随f的增加, 膜表面微孔尺寸逐渐减少, 微孔密度逐渐增加. 膜层主要由锐钛矿和金红石相TiO2及少量不饱和氧化物TiO2-x（0.02＜x＜0.07）相组成, 其中锐钛矿和金红石相TiO₂的相对含量随f的变化不明显, 而TiO_2-x的相对含量当f≤2 000 Hz时较高, 当f＞2 000 Hz时, TiO_2-x的相含量明显减少.      

Preparation and photo-catalytic activity of TiO2-coated medical stone-based porous ceramics

Medical stone-based porous ceramics as a carrier were prepared by ultra-fine grinding and low-temperature sintering method. Nano-TiO₂ thin films were loaded on the carrier by chemical liquid deposition method using titanium tetrachloride as a precursor. The micro-morphology and microstructure of the synthesized samples were characterized using X-ray diffraction, scanning electron microscopy with energy dispersive spectrometry, and mercury injection method. The photo-catalytic activity of the TiO₂ thin films was investigated by degrading formaldehyde. The main crystalline phase in the TiO₂ thin films calcined at 550°C is anatase with the average particle size about 10 nm. The specific surface area of the carrier-coated nano-TiO₂ increases from 3.68 to 5.32 m²/g. The formaldehyde removal rate of the TiO₂/medical stone-based porous ceramics irradiated under an ultraviolet lamp for 120 min reaches 85.6%.     

一步法合成SO42-/TiO2酸位结构及酯化机理研究

 利用高酸值麻疯树油中游离脂肪酸与甲醇酯化反应作为目标反应,通过直接煅烧工业原料偏钛酸,制得高酯化活性的ST(SO₄^2-/TiO₂)固体酸.FTIR研究表明:ST固体酸具有焦硫酸结构酸位,含有高键级高共价特性S=O.S=O强烈的诱导效应提高了与之相连的配位不饱和钛原子的路易斯酸性,吸水后产生质子酸.随着硫含量增加,质子酸性增加.ST固体酸制备过程中,硫酸根与二氧化钛发生固相反应,硫酸根强键合在二氧化钛表面,同时部分硫酸根分解产生三氧化硫并原位吸附,从而形成固体酸位.ST固体酸通过质子化羧酸、甲醇亲核加成、脱水脱质子机理催化酯化反应.对于麻疯树油中游离脂肪酸与甲醇的酯化反应,酸强度H0介于-12.70与-8.2之间的酸中心具有较好的催化活性.     

TiO2/SiO2复合光催化剂制备工艺参数优化及其表征

先以无机钛盐、硅酸盐为原料制取聚合硅酸硫酸钛,再通过液相水解法制得TiO2/SiO2复合光催化剂,并用SEM、XRD、BET和甲基橙脱色率对复合光催化剂进行表征。结果表明,TiO2/SiO2复合光催化剂制备优化工艺参数为:Ti(SO4)2作钛源、Ti/Si摩尔比为12∶1、水解反应pH值为6、煅烧温度为650℃,以此条件制备的复合光催化剂对甲基橙脱色率可达98.6%以上;TiO2/SiO2复合光催化剂为一种分散均匀的纳米级球形颗粒,其成分为以锐钛矿为主的TiO2,SiO2的复合有效抑制了TiO2晶粒的生长,同时提高了TiO2的热稳定性。     

Preparation of titanium dioxide from titania-rich slag by molten NaOH method

Preparing titanium dioxide from titania-rich slag (TiO₂ 73wt%) by molten NaOH method has been developed. The effects of temperature and reaction time on the titanium conversion were investigated. The results showed that temperature had significant influence on the titanium conversion as well as the structure of the product. About 92% of titanium in the titania-rich slag could be converted after reacting with NaOH at 500℃ for 1 h. Metatitanic acid was formed through the steps of washing treatment, acid dissolution, and hydrolysis. Well-dispersed spherical titanium dioxide particles with an average size of 0.1-0.4 μm can be obtained by calcination of metatitanic acid. In addition, the content of titanium dioxide in the product is up to 98.6wt%, which can be used as pigments after further treatment of coating and crushing.     

Phase transformation behavior of titanium during carbothermic reduction of titanomagnetite ironsand

The reduction of titanomagnetite (TTM) ironsand, which contains 11.41wt% TiO₂ and 55.63wt% total Fe, by graphite was performed using a thermogravimetric analysis system under an argon gas atmosphere at 1423–1623 K. The behavior and effects of titanium in TTM ironsand during the reduction process were investigated by means of thermogravimetric analysis, X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. During the reduction procedure, the titanium concentrated in the slag phase, where the phase transformation followed this sequence: FeO + FeTiO₃ → Fe₂TiO₄ → FeTiO₃ → FeTi₂O₅ → TiO₂. The calculated results for the reduction kinetics showed that the carbothermic reduction was controlled by the diffusion of ions through the product layer. Furthermore, the apparent activation energy was 170.35 kJ·mol-1.     

酸对TiO_2结构和光催化性能的影响

以H2SO4,HCl和一水合柠檬酸作酸催化剂,采用溶胶-凝胶法合成了纳米TiO2光催化剂。通过XRD,TEM,HR-TEM,Uv-Vis和FT-IR等分析手段对样品进行表征。以亚甲基蓝(MB)为目标降解物,对催化剂的光催化性能进行评价。研究结果表明,酸对TiO2的结构和性能有很大的影响:以H2SO4做催化剂时,TiO2颗粒分布均匀,粒径在7~12nm之间,全为锐钛矿相;以HCl作催化剂时,TiO2的粒径约为20nm,全为锐钛矿相;而以一水合柠檬酸作催化剂时,TiO2的粒径较大,约为30nm,且团聚严重,为锐钛矿相和金红石相的混合相。以H2SO4作催化剂制备的TiO2光催化活性最好。     

Environmentally-friendly harvesting TiO2 nanospheres and V2O5 microrods from spent selective catalytic reduction catalysts

Spent selective catalytic reduction (SCR) catalysts are defined as hazardous wastes because of the toxicity of V₂O₅ to the ecological environment. Recycling of V₂O₅ and TiO₂ from the spent SCR catalysts has strikingly social and environmental benefits as well as economic values. In this work, a “NaOH ​+ ​Na₂CO₃” system was employed to recycle 99.2% of anatase/rutile TiO₂ nanospheres with a nanospherical morphology from the spent SCR catalysts by a simple sintering-leaching process. The observed photocatalytic performance of anatase/rutile TiO₂ nanospheres was higher than that of the other TiO₂ recovered from the spent SCR catalysts, commercial TiO₂, and chemosynthetic TiO₂, which can be ascribed to the enhanced separation of photo-excited electron/hole in a direct Z-scheme of anatase/rutile TiO₂ homostructures. Additionally, high-purity V₂O₅ microrods with high H₂S removal performance were efficiently prepared by a hydrothermal method in the leaching solution, which is superior to the traditional method including NH₄VO₃ precipitation and solvent extraction as the present method can recycle vanadate from low-grade filtrate with a 99.6% of recovery rate. This study develops an alternative method for controlling pollution of vanadate to soil and water and recycling of valuable metals.     

硫酸法钛白生产中自生晶种水解过程的研究(金红石型颜料钛白粉研制报告之二)

本文研究了硫酸钛酰溶液的自生品种水解法。在一定条件下将钛液逐步加入热水体,可以生成晶粒直径分布良好的二氧化钛晶种。利用这种品种,可以在常压下水解高浓度钛液,再经相应的处理,可以制造性能优良的金红石型颜料钛白粉。     

恐龙化石的人工加速腐蚀研究

为了深入探讨恐龙化石的风化原因,为恐龙化石新型保护材料的研制提供理论支持,项目采用0.5,1,2mol/L硫酸溶液,二氧化碳饱和液与5%碳酸氢钠溶液对自贡出土恐龙化石进行人工加速腐蚀实验;利用失重法、XRD、XRF和显微法表征.结果表明:3种介质对化石腐蚀速率依次为硫酸溶液24.213 6g/(m2·h),二氧化碳0.663 7g/(m2·h),碳酸氢钠0.126 3g/(m2·h).硫酸溶液对化石腐蚀速率是二氧化碳的36.5倍,是碳酸氢钠溶液的191.7倍;在0.5mol/L硫酸溶液腐蚀下,XRD和XRF说明化石中CaCO3首先腐蚀,腐蚀量最大,腐蚀后化石中钙含量减少66.4%.化石腐蚀前后形貌变化与腐蚀速率一致.     

Synthesis of TiO2 supported on activated carbon by MOCVD： operation parameters study

The metallo-organic chemical vapor deposition (MOCVD) technique has been applied to the preparation of the photocatalyst titanium dioxide supported on activated carbon. The effects of various condition parameters such as carrier gas flow rate, source temperature and deposition temperature on the deposition rate were investigated. The maximum deposition rate of 8.2 mg/(g x h) was obtained under conditions of carrier gas flow rate of 400 ml/min, source temperature of 423 K and deposition temperature of 913 K. The deposition rate followed Arrhenius behavior at temperature of 753 K to 913 K, corresponding to activation energy E(a) of 51.09 kJ/mol. TiO(2) existed only in anatase phase when the deposition temperature was 773 K to 973 K. With increase of deposition temperature from 1073 K to 1273 K, the rutile content sharply increased from 7% to 70%. It was found that a deposition temperature of 773 K and a higher source temperature of 448 K resulted in finely dispersed TiO(2) particles, which were mainly in the range of 10-20 nm.     

培养单细胞蛋白的玉米芯水解条件研究

通过单因素搜索和正交实验对以 Ｃａｎｄｉｄａ ｂｏｉｄ ｉｎｉｉ Ｎｏ２２０１ 之诱变株 Ｙ－ １０８ 利用玉米芯水解液生产 Ｓ Ｃ Ｐ 的酸水解工艺进行了研究。本文报道了玉米芯原料酸水解工艺中,预处理方式、料液比、水解温度、时间、酸浓度等对水解还原糖得率和细胞产量的影响,结果表明,适宜的酸水解条件为 １∶８ 的料水比、１５％ 的硫酸、在 １２０℃的温度下直接水解 ３ｈ,其还原糖得率高达 ４３％ 左右,菌体产量平均在２３ｇ／ Ｌ。