固体超强酸（SO4^2-／ZrO2）的异丁烷／1-丁烯烷基化反应性能和失活研究

研究了固体超强酸(SO4^2-／ZrO2)催化剂的酸性及异丁烷-1-丁烯烷基化反应性能，结果表明，固体超强酸的酸性与焙烧温度有关，适当提高焙烧温度有利于样品酸强度的提高，但焙烧温度过高会导致脱硫，使样品酸强度和酸量降低，固体超强酸的异丁烷／1-丁烯烷基化催化反应活性与其酸性相对应，酸性强，反应活性高，但催化剂的活性衰减很快，这是催化剂表面的快速积炭所致。     

Pt-SO42-/ZrO2固体超强酸上异丁烷与丁烯烷基化反应

由异丁烷和1-丁烯烷基化合成高辛烷值汽油虽已被广泛用于工业生产,但由于液体酸催化剂存在许多缺点,寻找固体酸催化剂——分子筛、磺酸树脂及固体超强酸已受到国内外学者的广泛重视。对超强酸的研究多集中在SO_4~(2-)/氧化物催化剂上,此类催化剂的酸强度高、热稳定性好、制备简单,对异丁烷、1-丁烯烷基化具有较高的反应活性,但存在着积炭、寿命     

固体超强酸在异丁烷/丁烯烷基化反应中的再生研究

催化剂再生对于固体酸异丁烷／丁烯烷基化反应是必需的．虽然Broensted-Lewis共轭固体超强酸在温和条件下即对异丁烷／丁烯烷基化反应有良好的反应活性，但它仍象其它所有固体酸催化剂一样，面临着失活的问题．最主要的失活原因是积炭前身物生成并在催化剂表面的沉积，导致催化剂表面活性中心被覆盖．据此进行的再生方法研究集中在消除这些积炭前身物，本文中选择使用的是洗涤再生法，结果表明该方法对于该固体超强酸的再生在一定程度上是有效的。     

WO3/ZrO2固体强酸催化剂上异丁烷-丁烯烷基化反应的研究Ⅲ. 超细ZrO2载体对催化剂性能的影响

制备了以超细ZrO2为载体的WO3/ZrO2、 SO4 2-/ ZrO2、 MoO3/ZrO2固体强酸催化剂 ,并用XRD、 DTA-TG 、 H2-TPR、 NH3-TPD等方法表征了其晶型结构、表面状态和酸性. 结果表明,超细ZrO2及其催化剂均主要以T-晶相存在,与通常以Zr(OH)4为载体制备的同类催化剂相比,ZrO2中的T-晶相所占比例虽有所下降,但具有更大的比表面积、酸强度和对金属氧化物的负载能力,且酸强度随焙烧温度升高而增强,表明其表面状态亦有较大变化. 研究了以超细ZrO2为载体的固体强酸催化剂上, 异丁烷-丁烯的烷基化反应,与通常以Zr(OH)4为载体制得的催化剂相比,其具有更好的烯烃转化率,在烷基化产物中, C5～C7裂解产物较多,使C80的选择性有所下降.     

WO3/ZrO2固体强酸催化剂上异丁烷-丁烯烷基化反应研究(Ⅰ)--钨负载量和焙烧温度的影响

制备了系列 WO3/ Zr O2 固体强酸催化剂 ,用 XRD,DTA-TG,H2 -TPR,Raman光谱和酸性测定等方法测定其晶型结构、表面状态和酸性 .结果表明 ,WO3/ Zr O2 中的 Zr O2 基本以 T晶相存在 ,WO3对稳定 T晶相有重要作用 ,样品具有较大的表面积 .分散于 Zr O2 表面上的 WO3主要以单层分散和析出的 WO3晶粒形式存在 ,部分可能与 Zr O2 作用形成 Zr— O—W键并起强酸作用 .研究了各种实验条件下的异丁烷 -丁烯烷基化反应 .与其它固体酸相比 ,具有较高的起始活性和 i-C08选择性 ,且与酸强度和酸量有较好的对应关系     

异丁烷-丁烯烷基化反应催化剂的研究

固体强酸;异丁烷-丁烯烷基化反应催化剂的研究     

焙烧温度对纳米级SO2- 4/TiO2固体超强酸性能的影响

用锐钛型纳米TiO2制备了纳米级SO2- 4/TiO2固体超强酸,考查了焙烧温度对酸强度、比表面积、红外光谱及其催化活性的影响.结果显示该催化剂在450℃焙烧3 h,可以形成纳米级SO2-4/TiO2固体超强酸的结构.用该催化剂催化乙酸和丁醇酯化反应可使酯化率达到98.4%.     

多级孔结构WO3/ZrO2固体酸催化剂的烷基化催化性能研究

采用复合模板表面活性剂辅助水热法一步合成WO3/ZrO2体系多级孔固体酸催化剂,探讨了煅烧温度对所合成催化剂试样酸强度及酸量的影响,并考察了催化剂针对苯和十二烯的烷基化反应中的催化性能.结果表明,WO3/ZrO2体系催化剂具有较强的酸强度,并且与催化剂的比表面积和晶化程度有密切关系,比表面积的增大和四方相ZrO2的生成能有效地提高催化剂的酸强度.该催化剂具有优良的烷基化反应催化活性和选择性,其中450℃,5h煅烧的WO3/ZrO2催化剂样品酸性最强,其烷基化催化活性和选择性最优.     

焙烧温度对纳米级SO_4~(2-)/TiO_2固体超强酸性能的影响

用锐钛型纳米TiO2制备了纳米级SO42-/TiO2固体超强酸,考查了焙烧温度对酸强度、比表面积、红外光谱及其催化活性的影响.结果显示该催化剂在450℃焙烧3 h,可以形成纳米级SO42-/TiO2固体超强酸的结构.用该催化剂催化乙酸和丁醇酯化反应可使酯化率达到98.4%.     

WO3/ZrO2固体酸催化苯与1-己烯烷基化反应

 用浸渍法制备了WO3/ZrO2及碱金属K或碱土金属Sr掺杂改性的WO3/ZrO2固体酸催化剂. 采用X射线衍射、 N2吸附、 NH3程序升温脱附和吸附吡啶的红外光谱等技术表征了K或Sr对WO3/ZrO2催化剂结构和表面酸性质的影响. 研究了WO3/ZrO2及K或Sr掺杂改性的WO3/ZrO2固体酸对苯与1-己烯烷基化反应的催化性能. 考察了催化剂制备条件和反应条件对催化剂活性的影响以及催化剂的重复使用性. 结果表明,引入K或Sr可调变WO3/ZrO2固体酸中的ZrO2晶相和固体酸的酸强度、酸量以及Lewis酸中心与Brnsted酸中心的比值. 适量K或Sr掺杂改性可提高WO3/ZrO2催化剂对苯与1-己烯烷基化反应的催化活性和稳定性,在常压和80 ℃的温和条件下,反应10 min后, 1-己烯的转化率可达99%, 单烷基选择性为100%. 该催化剂可多次重复使用,催化活性稳定.     

Solvent extraction separation of In/III/-Tl/III/ and Hg/II/-Cd/II/-Co/II/ with sulphoxides

Solvent extraction studies have been made on some metals: In/III/-Tl/III/ and Hg/II/-Cd/II/-Co/II/, from ammonium thiocyanate solutions by dialkyl sulphoxides. Separation of these metals from one another can be achieved by suitable choice of the extracted conditions. The nature of the extractable metal species has been elucidated.     

Synthesis of chlorobis/β-diketonato/oxotechnetium/V/ and tris/β-diketonato/technetium/III/ complexes

Chlorobis/-diketonato/ oxotechnetium/V/ complexes [TcOCl/-dik/₂, -diketone=acetylacetone, benzoylacetone and dibenzoylmethane] were newly synthesized using macroamount of⁹⁹Tc. These complexes were further separated into geometrical isomers. Furthermore, an improvement of the yields for the syntheses of tris/-dike-tonato/technetium/III/ complexes [Tc/-dik/₃, -diketone=acetylacetone, benzoylacetone and 2-thenoyltrifluoroacetone] was examined using Tc/III/-thiourea complexes as a starting material.     

Crystal structure of Na3PO4 · 12H2O

The crystal structure of trisodium monophosphate hemihydrate was determined. The space group is $\text{C2}\text{c}$ and a unit cell contains eight formula units. The unit cell dimensions of $\text{Na}{}_3\text{PO}{}_4\text{·}\text{1}\text{2}\text{H}{}_2\text{O}$ are a = 9.631(3), b = 5.416(2), c = 16.938(8) Å, β = 102.60(5)°. The final R value is 0.027 for a set of 1430 independent reflections. This atomic arrangement is mainly a three-dimensional network of distorted NaO₆ octahedra. The hydrogen bonding scheme is given.     

Simultaneous propane dehydrogenation andco2hydrogenation overCrOx/SiO2catalyst

Summary Single reverse water-gas shift (RWGS) and dehydrogenation of propane with CO₂(DH-CO₂) reactions in the presence and absence of the CrO_x/SiO₂ catalyst have been studied between 673 and 873 K. It was found that the CrO_x/SiO₂ catalyst is active both in the dehydrogenation of propane and in the RWGS reactions. The obtained results suggest that the dehydrogenation of propane to propene in the presence of CO₂on CrO_x/SiO₂can be facilitated by the RWGS reaction.</o:p>     

Direct synthesis of dimethyl carbonate ?from CH3OH AND CO2 by H3PW12O40/CexTi1-xO2 catalyst

Summary Ce_xTi_1-xO₂ and H₃PW₁₂O₄₀/Ce_xTi_1-xO₂ catalysts were prepared using a sol-gel method, and applied to the direct synthesis of dimethyl carbonate from methanol and carbon dioxide. H₃PW₁₂O₄₀/Ce_xTi_1-xO₂ showed a better catalytic performance than the corresponding Ce_xTi_1-xO₂, due to the bifunctional catalysis of Br?nsted acid sites (provided by H₃PW₁₂O₄₀) and base sites (provided by Ce_xTi_1-xO₂). H₃PW₁₂O₄₀/Ce_0.1Ti_0.9O₂ showed the highest catalytic performance among the H₃PW₁₂O₄₀/Ce_xTi_1-xO₂ catalysts.     

Oxygen defect K2NiF4-type oxides: The compounds La2−xSrxCuO4−x2+δ

Oxygen defect K₂NiF₄-type oxides $\text{La}{}_{\mathrm{2?x}}\text{Sr}{}_{\mathrm{x}}\text{CuO}{}_{\mathrm{<mtext>4?</mtext><mtext>x</mtext><mtext>2</mtext><mtext>+\delta </mtext>}}$ have been synthesized for a wide composition range: 0 ≤ x ≤ 1.34. From the X-ray and electron diffraction study three domains have been characterized: orthorhombic compounds with La₂CuO₄ structure for 0 ≤ x < 0.10, tetragonal oxides similar to LaSrCuO₄ for 0.10 ≤ x < 1 and several superstructures derived from the tetragonal cell ( with n = 3, 4, 4.5, 5, 6) for 1 ≤ x ≤ 1.34. The compounds corresponding to 0 < x < 1 differ from the other oxides in that they are characterized by the presence of copper with two oxidation states: + 2 and + 3. A model structure for La_0.8Sr_1.2CuλO_3.4, in which copper has only the + 2 oxidation state, and for which the actual cell is tegragonal—a = 18.80₄ Å and c = 12.94 Å—has been established. The particular structural evolution of these compounds is discussed in terms of a competition between the capability of Cu(II) to be oxidized to Cu(III) and the ordering of oxygen vacancies.     

An investigation of the promotional effect of propylene or propane traces on the activity of sulfatedPt/g-Al2O3andPt-Sn/g-Al2O3inCH4combustion

Summary A strong promoting effect of the presence of C₃H₈or C₃H₆was determined for the combustion of CH₄in excess oxygen, over pre-sulfated 1%Pt/g-Al₂O₃and pre-sulfated 1%Pt-2%Sn/g-Al₂O₃catalysts.</o:p>     

A study of the spinel materials LiTi2O4 and Li43Ti53O4 by photoelectron spectroscopy

HeI-excited valence-band ultraviolet photoelectron spectra and MgKα-excited Ti-2p X-ray photoelectron spectra are reported for the spinel materials LiTi₂O₄ and $\text{Li}{}_{\mathrm{<mtext>4</mtext><mtext>3</mtext>}}\text{Ti}{}_{\mathrm{<mtext>5</mtext><mtext>3</mtext>}}\text{O}{}_4$. The presence of a Fermi edge in the ultraviolet photoelectron spectrum of LiTi₂O₄ confirms the metallic nature of this material, although the measured density of states at the Fermi energy is much lower than that expected from an independent-electron interpretation of the magnetic susceptibility. This difference is attributed to a strong interaction of the conduction electrons with the lattice vibrations. The localization of conduction electrons that occurs in the final state in the Ti-2p X-ray photoelectron spectrum of LiTi₂O₄ is attributed to a Coulomb interaction with a core hole.     

LixZryOz三元化合物的制备及表征

采用高温固相法制备了4种高纯度晶相组成的LixZryOz三元化合物,研究了焙烧温度、时间、反应物的种类和初始反应物物质的量比对产物组成的影响,进一步用XRD、SEM及BET分析方法对产物的晶相结构、表面形貌及比表面积进行了表征.实验结果表明,Li2CO3与ZrO2在适当条件下可以合成得到单斜相Li3ZrO3;以LiOH替代Li2CO3,在适当条件下可以分别合成得到四方相Li2ZrO3和三斜/单斜相Li6Zr2O7;进一步以Zr(NO3)4·5H2O代替Zr02,可将单斜相Li6Zr2O7的制备时间由96 h缩短至24 h.SEM照片显示产物硬团聚明显,粒径分布在1～10μm间,BET分析表明样品比表面积处于1.0～9.0 m2·g-1间分布,反应过程中锂的过量以及长时间高温焙烧是引起产物粒径长大和产生硬团聚的主要原因.     

Synthesis and characterization of Ti1−2xNbxNixO2−x/2 solid solutions

Doped-rutile has been traditionally used in ceramic pigments for its intense optical properties. In this paper, we compare the classical ceramic synthesis of Ti_1−2xNb_xNi_xO_2−x/2 system with the sol-gel methodology, which allows a reduction of the anatase-rutile transformation temperature. The composition was optimised in order to obtain a unique rutile phase with the minimum amount of pollutant Ni(II) and enhanced chromatic coordinates. Incorporation of the doping ions in the rutile structure was corroborated by XRD and Rietveld refinements. The species responsible for the colour mechanism were studied by different techniques. UV-VIS spectroscopy showed the characteristic features of Ni²⁺ ions, whose existence was corroborated by EPR and magnetic measurements. From these results, (Ni,Nb)doped-TiO₂ powder samples can be now shaped as thin films, monoliths, etc. by using sol-gel methodology without modifying their properties. This study introduces new possibilities of coloured TiO₂-based solid solutions in new combined advanced applications (colouring agent and photocatalyst, etc.).