低碳烯烃合成C12-C18的ZrZSM-5分子筛催化剂及制备方法

本发明公开了一种低碳烯烃合成Ｃ↓［１２］－Ｃ↓［１８］的ＺｒＺＳＭ－５分子筛催化剂及制备方法，催化剂的重量百分比组成为：Ｚｒ：２．０～７．０％，ＺＳＭ－５分子筛９３．０～９８．０％，所述的ＺＳＭ分子筛是Ｓｉ／Ａｌ摩尔比为２４～７８的氢型ＺＳＭ－５分子筛，采用在酸性溶液中进行离子交换而将Ｚｒ离子引入沸石中对其物性进行调整，使分子筛的强酸活性中心向中强酸的弱酸中心调变。在相同的反应条件下改质后齐聚反应的活性和Ｃ↓［１２］～Ｃ↓［１８］的选择性均有增加，Ｃ↓［１２］～Ｃ↓［１８］的择性由４０％增加至７８％左右，使低碳烯烃合成柴油成为可能。

The oxidative demethylation of 24-membered hexa-aza macrocyclic bicopper(I) complex - The mimicking for monooxygenase

By [2 + 2] Schiff base condensation of 5 - bromo - 2 - methoxylbenzene - 1,3 - dicarboxaldehyde with diethylenetriamine, a new hexaaza 24 - membered macrocyclic ligand was obtained,which formed a macrocyclic binuclear copper(I) complex in the presence of [Cu . (CH3CN)(4)]ClO4. When the copper(I) complex was oxidized in air or oxygen, a new macrocyclic binuclear copper( II) complex was obtained. The copper( II.) complex was characterized by several methods and its oxidized products was characterized by H-1 NMR. The results show that during oxidation, a methoxyl group in the ligand ring broke; and the phenoxy - and water - bridged Cu(II) complex formed. In oxidation of monooxygenase such as ligninase, oxidative demethylation also happened. Therefore this work mimicked this process for the first time by using macrocyclic complex. The quantity of absorbed oxygen and the absorption rate of oxygen were determined.

A NEW TOPOLOGICAL INDEX FOR RESEARCH ON STRUCTURE-PROPERTY RELATIONSHIPS OF ALKANES

in this Raper, based on distance matrix and branch vertex of atomes in a molecule, a new topological index (Y(x)) has been developed to be used in research on physical and chemical properties of alkanes. It is concluded that this index bears good structure selectivity and relativity when the results from index were compared with that of other ones.

Palaeoenvironmental changes from pollen record in deep sea core PC-1 from northern Okinawa Trough, East China Sea during the past 24 ka

A pollen record of core PC-1 from the northern Okinawa Trough, East China Sea (ECS), provides information on vegetation and climate changes since 24 cal. kaBP. A total of 103 samples were palynologically analyzed at 8 cm intervals with a time resolution of 230 a. Four pollen zones are recognized: zone I (812-715 cm, 24.2-21.1 cal. kaBP), zone II (715-451 cm, 21.1-15.2 cal. kaBP), zone III (451-251 cm, 15.2-10.8 cal. kaBP), zone IV (251-0 cm, 10.8-0.3 cal. kaBP), corresponding to Late MIS 3, Last Glacial Maximum (LGM), deglaciation and Holocene, respectively. The LGM is characterized by the dominance of herbs, mainly Artemisia, and high pollen influx, implying an open vegetation on the exposed continental shelf and a cool and dry climate. The deglaciation is a climate warming stage with Pinus percentage increased and Artemisia percentage decreased and a rapid sea-level rise. The Holocene is characterized by predominance of tree pollen with rapid increase in Castanea-Castanopsis indicating the development of mixed evergreen and deciduous broad-leaved forest and a warm, humid climate. Low pollen influx during the Holocene probably implies submergence of the continental shelf and retreat of the pollen source area. The vegetation indicated by pollen assemblage found in this upper zone is consistent with the present vegetation found in Kyushu, Japan. Originating from the humid mountain area of North Luzon of the Philippines, Tasmania and New Zealand, Phyllocladus with sporadic occurrence throughout PC-1 core probably suggests the influence of Palaeo-Kuroshio Current or intense summer monsoon. The observed changes in Pinus and Herbs percentage indicate fluctuations of the sea level, and high Pinus percentage corresponds to high sea level. Spectrum analysis of the pollen percentage record reveals many millennial-scale periodicities, such as periodicities of 6.8, 3.85 2.2, 1.6 ka.

Sources and preservation of organic matter in Plum Island salt marsh sediments (MA, USA): long-chain n-alkanes and stable carbon isotope compositions

Elemental (TOC, TN, C/N) and stable carbon isotopic (delta(13)C) compositions and n-alkane (nC(16-38)) concentrations were measured for Spartina alterniflora, a C-4 marsh grass, Typha latifolia, a C-3 marsh grass, and three sediment cores collected from middle and upper estuarine sites from the Plum Island salt marshes. Our results indicated that the organic matter preserved in the sediments was highly affected by the marsh plants that dominated the sampling sites. delta(13)C values of organic matter preserved in the upper fresh water site sediment were more negative (-23.0+/-0.3) as affected by the C-3 plants than the values of organic matter preserved in the sediments of middle (-18.9+/-0.8) and mud flat sites (-19.4+/-0.1) as influenced mainly by the C4 marsh plants. The distribution of n-alkanes measured in all sediments showed similar patterns as those determined in the marsh grasses S. alterniflora and T. latifolia, and nC(21) to nC(33) long-chain n-alkanes were the major compounds determined in all sediment samples. The strong odd-to-even carbon numbered n-alkane predominance was found in all three sediments and nC(29) was the most abundant homologue in all samples measured. Both delta(13)C compositions of organic matter and n-alkane distributions in these sediments indicate that the marsh plants could contribute significant amount of organic matter preserved in Plum Island salt marsh sediments. This suggests that salt marshes play an important role in the cycling of nutrients and organic carbon in the estuary and adjacent coastal waters. (C) 2003 Elsevier Ltd. All rights reserved.

中国南方热带地区田洋玛珥湖24万年以来的气候变化及湖泊演变

A continuous long (224m) and high-resolution core TY2 was recovered from paleo-maar-lake Tianyang, tropical South China. Based on the diatom records of the upper 130-m core, this paper focuses on exploring climate change and the lake evolution history in tropical South China during the past 240ka. The most typical and unique characteristics of the diatom assemblages is that, Aulacoseira granulata was dominant or absolutely dominant species (80-90%) during most parts of the 130-m core, while Cyclotella stelligera var. tenuis and Fragilaria construens var. venter were subdominant species in only limited parts of the lower and upper core, respectively. Time scale is always the biggest problem for the study of TY2 core, so although diatom is seldom used for establishing time scale, here we attempt this by correlating the diatom-reconstructed temperature sequence with the time scale of ODP core 806B from Equatorial Western Pacific. Verified by the few most reliable ages from TY2 core and the parallel core TYl, a rather reasonable and reliable time scale was established. 01S 7/6 falls at the depth of 100m (ca. 194kaBP), OIS 6/5 at 75m (ca. 132kaBP), OIS 5/4 at 46m (ca. 75kaBP), OIS 4-3 at 35m (ca. 60kaBP). Qualitative and quantitative environmental reconstructions are made on the basis of diatom assemblage ecotype and EDDI dataset. Correlation of diatom-reconstructed temperature and moisture changes of Core TY2 with pollen-reconstructed temperature and rainfall sequence of Core TYl proves that the results are quite consistent in most periods. Thus the reconstruction results from diatom are quite reliable, and probably have a much higher resolution than pollen results. Combined with lithological and magnetic susceptibility variations, the diatom analysis reveals that, the general climate in tropical South China during the past 240ka was warm and wet. On the time scale of glacial-interglacial, warm and wet, cool and dry are not always synchronous. It was relatively warm-wet during the penultimate interglacial, cool-dry during the penultimate glacial, warm-dry during the last interglacial, and cooler-drier during the last glacial. In contrast, on the time scale of subglacial-subinterglacial scales, warm and dry, cool and wet corresponds very obviously, showing very clear 21-23 ka precession cycle. Analysis also shows that, the water of Tianyang paleo-maar-lake was generally warm, turbulent, turbid, meso-trophic, slightly alkaline, low conductivity and fresh during the past 240 kaBP, with small variations in some parts. Tianyang paleolake experienced shallow to semi-deep lake in OIS7d, open shallow lake in OIS7c-OIS5b, shallow coastal lake in OIS5a-OIS4c, swamp in OIS4b, and then completely dried up in OIS3c. The lake evolution was mainly controlled by temperature and precipitation changes in tropical China. While temperature and precipitation changes were probably controlled by the migrations of monsoon rainband and the evaporation rate, which was in turn controlled by the evolution of East Asian monsoon. Therefore, when the summer monsoon was strongest the climate was warm-dry, when stronger the climate was warm-wet; when the winter monsoon was strongest the climate was cool-dry, stronger cool-wet. This mechanism caused the warm-dry sub interglacial and cool-wet subglacial climate in the tropical South China.

Development and application of oxygen permeable membrane in selective oxidation of light alkanes

In this paper, oxygen permeable membrane used in membrane reactor for selective oxidation of alkanes will be discussed in detail. The recent developments for the membrane materials will be presented, and the strategy for the selection of the membrane materials will be outlined. The main applications of oxygen permeable membrane in selective oxidation of light alkanes will be summarized, which includes partial oxidation of methane (POM) to syngas and partial oxidation of heptane (POH) to produce H-2, oxidative coupling of methane (OCM) to C-2, oxidative dehydrogenation of ethane (ODE) to ethylene and oxidative dehydrogenation of propane (ODP) to propylene. Achievements for the membrane material developments and selective oxidation of light alkanes in membrane reactor in our group are highlighted.

Alkanes-assisted low temperature formation of highly ordered SBA-15 with large cylindrical mesopores

Highly ordered SBA-15 silicas with large cylindrical mesopores (similar to 15 nm) are successfully obtained with the help of NH4F by controlling the initial reaction temperatures in the presence of excess amounts of alkanes.