甲烷氧化偶联Ti－La－Li系氧化物催化剂制备方法的研究

考察了用不同来源Ｌｉ（ＬｉＮＯ３和ＬｉＳＯ４）制备的催化剂催化的甲烷氧化偶联（ＯＣＭ）反应的特点，探讨了以ＬｉＮＯ３为锂源制备的催化剂的高温反应失活机理。ＸＲＤ、ＩＲ、ＸＰＳ和ＢＥＴ等方法的研究结果表明，以ＬｉＮＯ３为锂源制备的催化剂具有反应活性高、空速大的特点，而以Ｌｉ２ＳＯ４为锂源制备的催化剂具有Ｃ２选择性高、活性低、空速小等特点。由ＬｉＮＯ３制得的催化剂的失活原因是：在较高的反应温度下由于表面Ｌｉ的流失，使体相晶格中的Ｌｉ向表相扩散进而导致含Ｌｉ活性相ＬａＴｉ１－ｙＬｉｙＯ３－λ的分解（或部分分解），从而减少了体相和表相中氧空位的数量，导致催化剂的活性降低。设计了ＮＨ：（ＳＯ４）２浸渍法来固定表面锂。

STRUCTURE INVESTIGATION OF TI(OBU)4-ALET3 CATALYST BEFORE AND AFTER HEAT-TREATMENT

The catalyst structure of Ti(OBu)4-AlEt3 at different Al/Ti ratios before and after heat aging has been investigated from the data of UV, GC-MS, ESR and C-13 NMR spectra. The complex compounds formed by HTiEt2 and AlEt2(OBu) exist mainly in the catalyst solution, and no -OBu ligands linking with Ti atoms can be found at an Al/Ti ratio of four before heat aging. Many kinds of catalytic species with different size are formed after heat aging the catalyst at 110-degrees-C for 2 h. Dehydrogenation, accompanied by the valence change from Ti3+ to Ti2+, is observed during the aging process of the catalyst.

非晶态TiO_2-SiO_2网络缺陷和Ti配位结构的ESR研究

在SiO_2中掺杂其它原子会导致熔石英SiO_4四面体网络部分破坏,形成缺陷。主要缺陷有非桥氧,E′心和过氧基。非桥氧为仅与一个Si原子(或Ti原子)成单键的O原子。E′心为与三氧配位的Si原子。剩余一个未配对的印杂化电子形成悬键轨道。过氧基则为游离氧被非桥氧俘获,或非桥氧彼此俘获而形成的。这三种缺陷各有一个未配对电子,因而具有

Effect of Process Conditions on Microstructure and Corrosion Resistance of Cold-Sprayed Ti Coatings

Ti and Ti alloys can be applied to steels as a protective coating in view of its excellent resistance to corrosive environment. Cold spraying, as a new coating technique, has potential advantages in fabrication of Ti coating in comparison with conventional thermal spraying techniques. In this study, Ti coatings were prepared on carbon steel substrates by cold spraying via controlling the process conditions. The microstructure of coatings was observed by SEM. The porosity of coatings was estimated by image analysis and the bond strength was tested for comparison of the process conditions. Potentiodynamic polarization and open-circuit potential (OCP) measurements were performed to understand the corrosion behavior of the coatings. The SEM examination shows that the coatings become more compact with the increases of pressure and temperature of driving gas. The potentiodynamic polarization curves indicate that the coating which has lower porosity has lower corrosion current. The polarization and OCP measurement reveal that cold-sprayed Ti coating can provide favorable protection to carbon steel substrate. The polishing treatment of coating surface polishes the rough outer layer including the small pores as well as decreases the actual surface area of the coating, leading to the considerable improvement of corrosion resistance.

KEL-TI介质的地震波场响应与成像方法研究

To deal with the problems in multi-component converted seismic wave exploration in coal fields, the wave propagating features and imaging methods of multi-component converted waves in coal measure strata are researched in this thesis firstly. The relations between viscoelasticity and anisotropy in coal measure strata are analyzed to build KEL-TI model, and which seismic wave propagating and attenuating features are researched. The disadvantages of converted wave imaging methods based on common converted point gather are analyzed and constant velocity no NMO converted wave imaging method based on common scattering point gather is put forward, according to Huygens-Fresnel principle, which applicabilities in the elastic isotropic, elastic TI and KEL-TI situations are discussed. To different model simulation data, the common scattering point gathers’ and stacked profiles’ features are analyzed. The results show that the method can image compressional waves and converted waves with high precision. Secondly, the resolution enhancing theories and methods of converted wave are researched by Rayleigh wave suppressing, converted wave static correction and poststack inverse-Q filtering. 1) The polarization filter is designed by the instantaneous polarization information of seismic waves, and the Rayleigh wave suppressing method is researched. From the spectrum analysis before and after filtering, it can be derived that the amplitudes are kept relatively. 2) To constant velocity no NMO converted wave imaging method, the static correction method based on common equivalent offset point gather is put forward and tested to the actual converted waves. 3) The relation between equivalent quality factor of converted wave, compressional wave quality factor and the ratio of compressional to shear wave velocity is derived. The compressional wave quality inversion method by first arrivals of none-offset VSP is researched, and which is then transformed to the equivalent quality factor to perform inverse-Q filtering of actual converted waves. The result has shown that the method can recover the high frequency energy of converted waves. At last, the theories and methods researched in this thesis are practiced to the 3D3C seismic exploration in Guqiao coal mine in Huainan and achieve good results.

姚安和马厂箐富碱侵入岩体的地球化学特征

姚安岩体和马厂箐岩体属哀牢山-金沙江富碱侵入岩带的组成部分,位于NW-WNW向哀牢山-金沙江深大断裂东侧。姚安岩体主要为正长斑岩,马厂箐岩体主要为花岗斑岩两岩体化学成分上具有富碱、高钾的特点。岩石富轻稀土和Rb、Sr、Ba、Th、La等大离子亲石元素而亏损Nb、Ta和Ti等高场强元素。岩石的Rb/Sr、La/Nb和Ba/Nb以及LREE/HREE比值高,铕异常不明显,ISr值偏高,εNd值偏低。研究表明:(1)姚安岩体和马厂箐岩体形成于喜山期大陆弧伸展环境。两岩体的岩浆均起源于富集地幔(EMII),其壳幔混合特征,主要是俯冲带地幔楔内壳-幔物质源区混合的结果;(2)尽管姚安和马厂箐岩体在成岩构造背景、成岩时代、成岩方式和源区特征以及成分上高碱富钾等方面具相似性,但它们在岩性和组成上仍存在较大差异。这种差异可能是由源区物质部分熔融程度不同,以及岩浆结晶时温压和氧逸度等条件的不同所造成;(3)金矿化主要与相对高温、低压和高氧逸度的碱性系列岩浆活动有关,而铜矿化则主要与相对低温、高压和低氧逸度的碱性-亚碱性过度系列岩浆活动有关。

峨眉火成岩省岩浆矿床成矿作用与地幔柱动力学过程的耦合关系

峨眉火成岩省位于扬子地块西部，为中二叠世末地幔柱活动产物。迄今为止，峨眉火成岩省已发现超大型V—Ti磁铁矿矿床4处，大中型岩浆硫化物型Ni—Cu-（PGE）矿床近10处。这些矿床的含矿镁铁一超镁铁岩体为260Ma±，与峨眉山玄武岩为同一地幔柱的产物。系统归纳和分析上述两类含矿镁铁-超镁铁岩体在空间分布、岩体规模、岩石组合和造岩矿物组成等方面存在明显的差异：可以分为内带和外带，内带以巨厚的峨眉山玄武岩、大型层状岩体和众多小型镁铁-超镁铁岩体、低Ti玄武岩、碱性岩体和丰富的成矿作用为标志。外带则玄武岩厚度降低，以高-Ti玄武岩为主，很少有侵入岩体。在对这两类岩浆矿床的分布及其与低Ti和高Ti玄武岩地质和地球化学联系的归纳和分析基础上，结合对杨柳坪Ni—Cu-（PGE）硫化物矿床成矿过程与峨眉山玄武岩岩浆起源和演化相互关系的研究结果，认为峨眉山火成岩省这些不同类型的矿床是地幔柱动力学过程不同阶段的产物。V—Ti磁铁矿矿床的形成于高Ti玄武岩浆有关，主要受控于岩浆的分离结晶作用；而Ni—Cu-（PGE）硫化物矿床成矿主要取决于3个因素：高程度的部分熔融，下地壳同化混染和分离结晶。Ni—Cu-（PGE）硫化物矿床是地幔柱活动早期阶段的产物，而V—Ti磁铁矿矿床则形成则晚于岩浆硫化物矿床。

胶北晚中生代煌斑岩的岩石地球化学特征及其成因研究

胶北煌斑岩分别采自龙口、烟台和威海地区，包括拉辉煌斑岩、斜闪正煌岩和角闪煌斑岩，煌斑岩K—Ar全岩年龄变化于89．3～169．5Ma，为晚中生代岩浆活动的产物。在岩石化学组成上，SiO2=42．02％～54．95％，以钙碱性系列为主．岩石以富集大离子亲石元素（LILE）（Ba，U，K，Th）和LREE，亏损高场强元素（HFSE）（Nb，Ta和Ti）为特征，Mg^#=33．9～53．9，Eu／Eu^＊=0．71～0．89，^87Sr／^86Sr初始比值0．707642～0．709791，εNd（t）为-17．6～-10．4，^206Pb／^204Pb=37．588～38．431，^207Pb／^204Pb=15．423～15．531，^206Pb／^204Pb=17．204～18．179。表明煌斑岩源自俯冲陆壳（扬子下地壳）在地幔源区发生交代作用时形成的富集型地幔的部分熔融体．考虑到煌斑岩具有大陆边缘弧玄武岩的特征，我们认为煌斑岩在成因上同样与古大洋板块的俯冲作用有关，为碰撞后弧岩浆作用形成的脉岩。

鲁西晚中生代基性脉岩的成因和源区性质：岩石学和地球化学

本文从岩石学和地球化学方面对鲁西地区淄博盆地几个岩区的基性脉岩的成因和源区性质进行了探讨。脉岩的K-Ar年龄(72．2～116．3 Ma)表明其为晚中生代(白垩纪)岩浆作用的产物。主量元素显示该脉岩总体属钙碱性系列。微量元素特征表明脉岩为交代富集地幔部分熔融作用的产物，成岩过程可能同时经历了橄榄石、单斜辉石、Ti-Fe氧化物以及少量斜长石的分离结晶作用。Pb同位素组成：^208Pb／^204Pb=36．308～38．329；^207Pb／^204Pb=15．170～15．632；^206Pb／^204Pb=16．658～18．470，可以和下地壳组成相比，暗示成岩过程中存在大量下地壳物质的参与。岩浆在构造上受控于燕山造山带坍塌和沂沭断裂带(郯庐断裂山东段)的活动(左行平移和伸展)，但在上升侵位过程中没有遭受地壳物质的混染，且具有大陆边缘弧玄武岩的特性。这暗示岩浆早期鲁西地区存在古大洋板块(苏-鲁洋)的俯冲作用(即古俯冲作用)。

闽东南基性岩脉成因及动力学背景研究：Sr-Nd同位素、元素地球化学

闽东南的海边斜闪煌斑岩脉和赤湖辉长岩脉分别形成于晚白垩世和古新世,为高钾钙碱性和钙碱性系列岩石,具有高Al、Na2O＞K2O的特征;岩浆演化过程中可能经历了以橄榄石、单斜辉石为主的结晶分异作用.海边和赤湖基性岩脉具有相对富集大离子亲石元素和轻稀土元素,亏损高强场元素特征,不相容元素蛛网图显示出大陆边缘弧的地球化学特征,以Nb、Ta、Ti负异常为特征;海边和赤湖明显富集轻稀土元素,（La/Yb）N分别为5.0～10.9和11.2～12.0.具有高Sr同位素初始值和低εNd（t）值,海边的（^87Sr/^86Sr）i：0.70577～0.707574,εNd（t）：-8.1～-1.8,赤湖的（^87Sr/^86Sr）i：0.70547～0.70552,εNd（t）：-0.2～0.6.根据Sr、Nd同位素、微量元素研究及野外地质观察,本区基性岩脉的岩浆在上升侵位过程中未发生地壳物质混染.通过Sr、Nd同位素和微量元素等研究,认为地幔源区的演化与古太平洋板块俯冲密切相关,俯冲流体交代地幔楔、消减洋壳携带的海洋与陆源沉积物参与地幔源区的混合,形成本区基性岩脉的富集地幔源区,大离子亲石元素和轻稀土元素特别富集是俯冲流体与沉积物共同参与源区演化的结果.海边和赤湖基性岩脉形成的构造背景属于活动大陆边缘弧,构造性质应为活动陆缘拉张带（或裂谷带）.晚白垩世和古新世,闽东南发生了地壳拉张事件,与中国东南部晚白垩世以来的地壳拉张期次是一致.

Epoxidation of propylene with dilute H2O2 over titanium silicalite containing trace aluminum

Titanium silicalite (TS-1) was successfully synthesized by using TPABr as the template and silica sol as silicon source in a 100 l stainless steel autoclave. IR, XRD, UV--vis, elemental analysis, and (2)7Al and (3)1P MAS NMR were used to characterize the synthesized products. The results show that the synthesized material has an MFI structure with high crystallinity and large crystal size and two kinds of titanium species. Trace aluminum in silica sol is also incorporated into the zeolite framework. The synthesized TS-1 exhibits high activity in the epoxidation of propylene with dilute H2O2 with high selectivity to methyl mono-ethers and low selectivity to propylene oxide (PO). The low selectivity toward PO is due to the residual acidity onto TS-1. The selectivity of PO can reach up to 90% through adjusting the pH of the reaction mixture. Extra amounts of base decrease the H2O2 utilization and the H2O2 conversion. However, in over acid-treated TS-1 in which part removal of extra-framework titanium takes place, the utilization of H2O2 is quite different: for the low Si/Ti ratio of TS-1, the H2O2 utilization increases. But the utilization of H2O2 does not change for the high Si/Ti ratio TS-1. Thermal analysis shows that the as-synthesized TS-1 exhibits high activity and thermal stability in the calcined range 540-900 degreesC.