太阳光/TiO2-γ-Al2O3光催化处理垃圾渗滤液的研究

采用液相共沉淀法制备了TiO₂-γ-Al₂O₃复合催化剂,在其最佳合成条件下,比较了太阳光/TiO₂-γ-Al₂O₃与UV/TiO₂处理垃圾渗滤液的性能。结果表明,当Ti（SO₄）₂与Al₂（SO₄）₃·18H₂O摩尔配比为1:2、聚乙二醇2000投加质量分数为1.25%、焙烧温度为650℃时,TiO₂-γ-Al₂O₃的催化活性最强。当催化剂投加量与垃圾渗滤液COD质量比为1.75、反应时间为90 min、渗滤液pH为3时,太阳光/TiO₂-γ-Al₂O₃对COD、NH₄⁺-N的去除率几乎达到最高,分别为81.97%和54.95%,...     

TiO2与SiO2掺杂对Al2O3相转变的研究

通过球磨混合法,制备TiO₂、SiO₂和TiO₂+SiO₂掺杂的Al₂O₃粉体,经不同温度煅烧后进行X射线衍射(XRD)测试,比较研究这三种掺杂对Al₂O₃粉体相转变温度的影响。研究结果表明,TiO₂、SiO₂掺杂对γ-Al₂O₃向α-Al₂O₃的相转变均有促进作用。在掺杂质量分数为0.5%的情况下,二者可分别使γ-Al₂O₃完全转变为α-Al₂O₃的温度降低100 ℃和125 ℃。而TiO₂+SiO₂复合掺杂对γ-Al₂O₃向α-Al₂O₃相转变的促进作用优于TiO₂、SiO₂单独掺杂。TiO₂、SiO₂的质量分数均为0.3%时,复合掺杂可使γ-Al₂O₃完全转变为α-Al₂O₃的温度降低150 ℃。此外,还对TiO₂、SiO₂和TiO₂+SiO₂掺杂促进Al₂O₃粉体相转变的机理作了简单分析。     

聚乙烯醇对溶胶—凝胶法氧化铝陶瓷膜制备的影响

为控制溶胶 - 凝胶法中的 AlOOH 溶胶涂膜工艺,以聚乙烯醇 (PVA) 为增稠剂调控 AlOOH 溶胶的流变性能,制得了 Al₂O₃陶瓷膜,并通过旋转流变仪、热重分析仪、SEM 表征 PVA 对 AlOOH 涂膜及 Al₂O₃陶瓷膜的影响。PVA 的加入量会增加 AlOOH 的黏度与假塑性,加快凝胶速率,从而使涂膜后的厚度增加;适量的 PVA 可使 AlOOH 粘附力更强,膜层更完整,当 PVA 加入量大于 0.5 wt% 时,因黏度太大而使涂膜不均而导致凝胶膜开裂。最适 PVA 加入量为 0.3wt%,此时 Al₂O₃膜最完整,厚度约为 9 μm,水通量为最低的 166.2 L/(m²·bar·h),通过 PVA 可以显著调节 AlOOH溶胶的涂膜效果。     

一维TiO2-Al2O3载体的制备及其在加氢脱氮中的应用

为提高现有负载型NiMoS催化剂的加氢活性,以碳纳米管为结构导向剂,分别采用浸渍法和溶胶-凝胶法制备了2种一维TiO₂-Al₂O₃载体,并采用共浸渍法制备了相应的负载型NiMoS催化剂,探究了不同结构的载体对NiMoS/TiO₂-Al₂O₃催化剂加氢脱氮性能的影响。结果表明,当选择以溶胶-凝胶法制备的一维TiO₂-Al₂O₃为载体时,NiMoS/TiO₂-Al₂O₃催化剂上的加氢脱氮活性较高,在350℃、氢压为3 MPa、转速为400 r/min的条件下反应4 h,喹啉的转化率达到99%以上,脱氮率达到40.75%。     

NiMo/TiO2-Al2O3催化剂活性相表征及加氢脱硫反应性能研究

采用共沉淀法制备TiO₂含量不同的TiO₂-Al₂O₃复合载体,以传统的浸渍法制备活性金属负载量相同的NiMo/TiO₂-Al₂O₃催化剂。运用N₂低温吸附法、X射线衍射、H₂程序升温还原和激光拉曼光谱等方法对催化剂进行表征,在10 mL微型反应装置上进行催化剂活性评价。结果表明,当复合载体中TiO₂含量达到一定值后,TiO₂在整个TiO₂- Al₂O₃体系中的存在状态由高度分散转变为表面富集,XRD能够检测出锐钛矿型TiO₂的特征峰;TiO₂的添加对于催化剂的酸性能没有明显改变;激光拉曼光谱分析结果表明,TiO₂的存在有利于生成八面体结构的钼物种,并在TiO₂质量分数为8%时加氢脱硫活性达到较高水平。     

TiO2-ZrO2聚合溶胶形成过程的小角X射线散射研究

由金属醇盐（M（OR）₄）水解制备溶胶的方法已广泛应用于溶胶-凝胶法制备纳米孔无机膜。通过控制异丙醇钛[Ti（i-OC₃H₇）₄]和正丙醇锆[Zr（n-OC₃H₇）₄]的混合物在异丙醇（i-C₃H₇OH）中水解制备聚合型TiO₂-ZrO₂溶胶,利用小角X射线散射方法（SAXS）研究了初始反应混合物Ti（i-OC₃H₇）₄：Zr（n-OC₃H₇）₄：H₂O：i-C₃H₇OH=0.9：0.1：m：30（摩尔比,m=1.8,2.0,2.2）形成TiO₂-ZrO₂溶胶的过程,探讨了水与醇盐摩尔比H₂O/M（OR）₄（M=Ti+Zr）、反应温度和正丙醇锆对TiO₂-ZrO₂溶胶形成的影响。研究结果表明,H₂O/M（OR）₄=1.8时,只有少量胶粒形成;H₂O/M（OR）₄=2.0～2.2时,TiO₂-ZrO₂溶胶中胶粒具有质量分形结构,分形维数1.2 ≤ D_m < 1.4;随着H₂O/M（OR）₄增加,胶粒的形成时间缩短,胶粒大小和分形维数均增大,溶胶的稳定性显著下降。升高反应温度有利于胶粒形成。[Ti（i-OC₃H₇）₄+Zr（n-OC₃H₇）₄]混合物比Ti（i-OC₃H₇）₄水解快,H₂O/M（OR）₄相同时,TiO₂-ZrO₂溶胶比TiO₂溶胶稳定性差。     

TiO2溶胶流变及涂膜性能的研究

以钛酸丁酯为原料,采用溶胶-凝胶法制备Ti(OH)₄溶胶。通过旋转流变仪作为主要表征手段,对Ti(OH)₄溶胶的黏度、流动性能、涂膜性能进行分析,研究了R(nCH₃COOH∶nH₂O)值对Ti(OH)₄溶胶流变特性的影响,阐述了溶胶流变性和涂膜性能的相关性。结果表明：当R逐渐增大至1.2～1.8时,Ti(OH)₄溶胶表现为Bingham流体,初始黏度从0.270 Pa·s下降至0.156 Pa·s,流动系数接近于水;在R值低于0.9时,Ti(OH)₄溶胶表现为HerschelBulkley流体,初始黏度从0.304 Pa·s上升至3.011 Pa·s,流动系数从0.724下降至0.419。在R=0.9时,涂膜效果最佳,膜厚度约为10μm,表面光滑完整,对结晶紫的去除率可达95.5%。     

Na2O掺杂铝酸钙化合物物相转化与浸出性能

以分析纯试剂CaCO₃、Al₂O₃和Na₂CO₃为原料,在1350℃烧结1 h合成了Na₂O掺杂铝酸钙熟料,并采用XRD、SEM和EDS等方法研究了Na₂O掺杂CaO-Al₂O₃体系铝酸钙化合物的物相演变规律及熟料浸出性能。结果表明:当CaO和Al₂O₃的摩尔比为1.0时,CaO-Al₂O₃体系铝酸钙由CaO·Al₂O₃和12CaO·7Al₂O₃组成,而Na₂O掺杂铝酸钙熟料由CaO·Al₂O₃、12CaO·7Al₂O₃、Na₂O·Al₂O₃和Na₄Ca₃(AlO₂)₁₀组成。除形成含Na₂O化合物外,熟料中掺杂的Na₂O固溶于12CaO·7Al₂O₃中,而CaO·Al₂O₃中几乎不含Na₂O。随着熟料中Na₂O掺杂量的升高,12CaO·7Al₂O₃和Na₄Ca₃(AlO₂)₁₀的含量逐渐增加,CaO·Al₂O₃的含量逐渐降低;12CaO·7Al₂O₃和Na₄Ca₃(AlO₂)₁₀的结晶度逐渐降低,CaO·Al₂O₃的结晶度逐渐升高。Na₂O的掺杂提高了熟料在碳酸钠溶液中的浸出性能,并且使浸出渣中CaCO₃的空间群由R-3CH、P63/MMC两种转变为只含有R-3CH一种。     

制备条件对Ni2P/TiO2-Al2O3催化剂加氢脱硫性能的影响

采用溶胶-凝胶法制备了TiO₂-Al₂O₃复合载体, 以柠檬酸为络合剂, 浸渍法制备了负载型Ni₂P/TiO₂-Al₂O₃催化剂前体, 程序升温H₂还原法制备了Ni₂P/TiO₂-Al₂O₃催化剂, 并用 X 射线衍射(XRD)、N₂吸附比表面积(BET)测定技术对催化剂的结构和性质进行了表征, 考察了浸渍方法、Ni/P摩尔比、Ni₂P负载量对其进行的二苯并噻吩(DBT)加氢脱硫(HDS)性能的影响。结果表明, 当Ni/P比低于1:1时, 能得到单一的Ni₂P物相;当Ni/P比为2:1时, 开始出现Ni₃P物相。采用Ni/P比为1:1、Ni₂P负载量为30%、采用共浸渍方法制备的Ni₂P/TiO₂-Al₂O₃催化剂具有最好的活性, 在360℃、3.0MPa、氢油比500 (体积比)、液时体积空速2.0h^-1的条件下反应4h时, 二苯并噻吩转化率为99.5%。     

Al2O3溶胶对铝基磷酸盐涂层组织及性能的影响

为提高铝基磷酸盐涂层的耐腐蚀性能和力学性能,通过在铝基磷酸盐涂料中添加 Al₂O₃溶胶,经空气喷涂与热固化得到 Al₂O₃颗粒增强铝基磷酸盐复合涂层,采用 X射线衍射仪（ XRD）、扫描电镜（ SEM）、胶粘拉脱法、维氏硬度、电化学腐蚀试验和模拟海水浸泡试验考察 Al₂O₃溶胶含量对复合涂层微观组织、力学性能和耐腐蚀性能的影响。结果表明： Al₂O₃溶胶在涂层 500 ℃热固化的物相演化为 Al₂O₃溶胶 -AlOOH-Al₂O₃,随 Al₂O₃溶胶含量从 0增加到（γ相）生成的 Al₂O₃颗粒在涂层呈弥散分布;4%,复合涂层的孔隙减少,致密性提高, Al₂O₃颗粒弥散强化作用得到发挥,涂层结合强度由 15 MPa提高为 25 MPa,硬度由 38 HV提高为 65 HV;添加 Al₂O₃溶胶制备得到的铝基磷酸盐复合涂层耐腐蚀性能明显提高,自腐蚀电流密度由 2. 38×10-7 A/cm2下降至 2. 79×10^-8 A/cm²,极化电阻由 1. 95×10⁴ Ω提升至 4. 73×10⁵ Ω。     

Pt/TiO_2催化二甲醚部分氧化重整制氢

二甲醚是一种理想的氢载体,可用于解决氢的储存和运输。以Pt/TiO_2为部分氧化催化剂,结合Ni/Al_2O_3重整催化剂,考察钛前驱体和焙烧温度对二甲醚部分氧化重整制氢反应的影响。结果表明,以Ti(C4H9O)4为原料制备的TiO_2为金红石相,Ti(SO4)2或Ti O(OH)2为原料制备的TiO_2为锐钛矿相;以Ti(C4H9O)4为原料制备的Pt/TiO_2-E催化剂催化性能略好,转化率接近100%,H2收率约90%,表明金红石相TiO_2负载的Pt催化剂略佳;以Ti(SO4)2为原料制备的Pt/TiO_2-S催化剂500℃焙烧可获得金红石相TiO_2。与Pt/Al_2O_3催化剂相比,Pt/TiO_2催化剂具有更好的催化性能,H2收率超过90%,而Pt/Al_2O_3催化剂H2收率约80%。     

CO_2 methanation over TiO_2–Al_2O_3 binary oxides supported Ru catalysts

TiO_2 modified Al_2O_3 binary oxide was prepared by a wet-impregnation method and used as the support for ruthenium catalyst. The catalytic performance of Ru/TiO_2–Al_2O_3catalyst in CO_2 methanation reaction was investigated. Compared with Ru/Al_2O_3 catalyst, the Ru/TiO_2–Al_2O_3catalytic system exhibited a much higher activity in CO_2 methanation reaction. The reaction rate over Ru/TiO_2–Al_2O_3 was 0.59 mol CO_2·(g Ru)1·h-1, 3.1 times higher than that on Ru/Al_2O_3[0.19 mol CO_2·(gRu)-1·h-1]. The effect of TiO_2 content and TiO_2–Al_2O_3calcination temperature on catalytic performance was addressed. The corresponding structures of each catalyst were characterized by means of H_2-TPR, XRD, and TEM. Results indicated that the averaged particle size of the Ru on TiO_2–Al_2O_3support is 2.8 nm, smaller than that on Al_2O_3 support of 4.3 nm. Therefore, we conclude that the improved activity over Ru/TiO_2–Al_2O_3catalyst is originated from the smaller particle size of ruthenium resulting from a strong interaction between Ru and the rutile-TiO_2 support, which hindered the aggregation of Ru nanoparticles.     

TiO2-coated on Al2O3 support prepared by the CVD method for HDS catalysts

Mo---Co or Mo---Ni catalysts supported on alumina (Al₂O₃) have been widely used for hydrodesulfurization (HDS) of heavy petroleum fractions. In order to enhance the catalytic activities for HDS, a composite type support (TiO₂-Al₂O₃) prepared by the chemical vapor deposition (CVD) method has been studied. We found that Mo catalyst supported on TiO₂-Al₂O₃ showed much higher catalytic activity for HDS of dibenzothiophene derivatives than the catalysts supported on Al₂O₃.     

异丙醇钛控制水解的小角X射线散射研究

由金属醇盐水解制备溶胶的方法已广泛应用于溶胶-凝胶法制备纳米孔无机膜,但对金属醇盐水解机理的认识十分有限。通过控制异丙醇钛[Ti（i-OC₃H₇）₄]在异丙醇（i-C₃H₇OH）中水解制备TiO₂溶胶,利用小角X射线散射（SAXS）方法研究了由不同H₂O/Ti（i-OC₃H₇）₄的反应混合物[Ti（i-OC₃H₇）₄：H₂O：i-C₃H₇OH=1：m：30（摩尔比）]形成TiO₂溶胶的过程,探讨了控制Ti（i-OC₃H₇）₄水解的过程中胶粒形成与长大的规律。研究结果表明,所合成的TiO₂溶胶的胶粒粒径小于10 nm,胶粒的形成和长大与H₂O/Ti（i-OC₃H₇）₄摩尔比密切相关。H₂O/Ti（i-OC₃H₇）₄（摩尔比） ≥ 2.0时,随着H₂O/Ti（i-OC₃H₇）₄增加,溶胶的稳定性下降。     

Al2O3@TiO2复合生物载体的制备及其BSA吸附特性

通过钛酸盐和氧化钛溶胶两种制备途径在氧化铝（Al₂O₃）支撑体外包覆介孔氧化钛（TiO₂）层,分析了这两种途径制备的氧化钛表面结构与性质的差异及其对于BSA蛋白吸附性能的影响。以粒径分别为0.37、10.4和21.8 mm的三种氧化铝支撑体作为基材,用XRD、Raman分析了两种路径制备的氧化钛晶型均为锐钛矿相;N₂吸脱附分析其比表面积均在（100±10）m²·g^-1,两者具有相似的介孔结构。FESEM分析发现钛酸钾溶胶制备的氧化钛的形貌受到支撑体孔径的影响。对于在牛血清蛋白（BSA）吸附实验中,钛酸钾溶胶法包覆的20 mm粒径复合载体（SP20@K-TiO₂）吸附量为22.18 mg·g^-1,高于相同条件下氧化钛溶胶制备的Al₂O₃@TiO₂复合载体。SP20@K-TiO₂ 中TiO₂吸附量为150.88 mg·g^-1,相比于TiO₂粉体,复合载体中TiO₂对BSA蛋白吸附的性能得到提升。     

Hydrodesulfurization of dibenzothiophenes over molybdenum catalyst supported on TiO2–Al2O3

Composite types of TiO₂–Al₂O₃ supports, which are γ-aluminas coated by titania, have been prepared by chemical vapor deposition (CVD), using TiCl₄ as a precursor. Then supported molybdenum catalysts have been prepared by an impregnation method. As supports, we employed γ-alumina, anatase types of titania, and composite types of TiO₂–Al₂O₃ with different loadings of TiO₂. We studied the conversion of Mo from oxidic to sulfidic state through sulfurization by X-ray photoelectron spectroscopy (XPS). The obtained spectra unambiguously revealed the higher reducibility from oxidic to sulfidic molybdenum species on the TiO₂ and TiO₂–Al₂O₃ supports compared to that on the Al₂O₃ support. Higher TiO₂ loadings of the TiO₂–Al₂O₃ composite support led to higher reducibility for molybdenum species. Furthermore, the catalytic behavior of supported molybdenum catalysts has been investigated for hydrodesulfurization (HDS) of dibenzothiophene (DBT) and methyl-substituted DBT derivatives. The conversion over the TiO₂–Al₂O₃ supported Mo catalysts, in particular for the 4,6-dimethyl-DBT, is much higher than that obtained over Al₂O₃ supported Mo catalyst. The ratio of the corresponding cyclohexylbenzene (CHB)/biphenyl (BP) derivatives is increased over the Mo/TiO₂–Al₂O₃. This indicates that the prehydrogenation of an aromatic ring plays an important role in the HDS of DBT derivatives over TiO₂–Al₂O₃ supported catalysts.     

Ti-modified alumina supports prepared by sol–gel method used for deep HDS catalysts

The typical physico-chemical properties and their hydrodesulfurization activities of NiMo/TiO₂-Al₂O₃ series catalysts with different TiO₂ loadings were studied. The catalysts were evaluated with a blend of two kinds of commercially available diesels in a micro-reactor unit. Many techniques including N₂-adsorption, UV–vis DRS, XRD, FT-Raman, TPR, pyridine FT-IR and DRIFT were used to characterize the surface and structural properties of TiO₂-Al₂O₃ binary oxide supports and the NiMo/TiO₂-Al₂O₃ catalysts. The samples prepared by sol–gel method possessed large specific surface areas, pore volumes and large average pore sizes that were suitable for the high dispersion of nickel and molybdenum active components. UV–vis DRS, XRD and FT-Raman results indicated that the presence of anatase TiO₂ species facilitated the formation of coordinatively unsaturated sites (CUS) or sulfur vacancies, and also promoted high dispersion of Mo active phase on the catalyst surfaces. DRIFT spectra of NO adsorbed on the pure MoS₂ and the catalysts with TiO₂ loadings of 15 and 30% showed that NiMo/TiO₂-Al₂O₃ catalysts possessed more CUS than that of pure MoS₂. HDS efficiencies and the above characterization results confirmed that the incorporation of TiO₂ into Al₂O₃ could adjust the interaction between support and active metals, enhanced the reducibility of molybdenum and thus resulted in the high activity of HDS reaction.