Polypropylene as a carbon source for the synthesis of multi-walled carbon nanotubes via catalytic combustion

Multi-walled carbon nanotubes (MWCNTs) were efficiently synthesized by catalytic combustion of polypropylene (PP) using nickel compounds (such as Ni2O3, NiO, Ni(OH)(2) and NiCO3 (.) 2Ni(OH)(2)) as catalysts in the presence of organic-modified montmorillonite (OMMT) at 630-830 degrees C. Morphologies of the sample undergoing different combustion times were observed to investigate actual process producing MWCNTs by this method. The obtained MWCNTs were characterized by X-ray diffraction (XRD), transmission electron microscope and Raman spectroscopy. The yield of MWCNTs was affected by the composition of PP mixtures with OMMT and nickel compounds and the combustion temperature. The proton acidic sites from the degraded OMMT layers due to the Hoffman reaction of the modifiers at high temperature played an important role in the catalytic degradation of PP to supply carbon sources that are easy to be catalyzed by nickel catalyst for the growth of MWCNTs. The XRD measurements demonstrated that the nickel compounds were in situ reduced into the Ni(0) state with the aid of hydrogen gas and/or hydrocarbons in the degradation products of PP, and the Ni(O) was really the active site for the growth of MWCNTs. The combination of nickel compounds with OMMT was a key factor to efficiently synthesize MWCNTs via catalytic combustion of PP.

Influences of catalysis and dispersion of organically modified montmorillonite on flame retardancy of polypropylene nanocomposites

The degradation and flame retardancy of polypropylene/organically modified montmorillonite (PP/OMMT) nanocomposite were studied by means of gas chromatography-mass spectrometry and cone calorimeter. The catalysis of hydrogen proton containing montmorillonite (H-MMT) derived from thermal decomposition of (alkyl) ammonium in the OMMT on degradation of PP strongly influence carbonization behavior of PP and then flame retardancy. Bronsted acid sites on the H-MMT could catalyze degradation reaction of PP via cationic mechanism, which leads to the formation of char during combustion of PP via hydride transfer reaction. A continuous carbonaceous MMT-rich char on the surface of the burned residues, which work as a protective barrier to heat and mass transfer, results from the homogeneous dispersion of OMMT in the PP matrix and appropriate char produced.

Synthesis of macrocyclic arylene ketone oligomers containing the phthaloyl moiety by Friedel-crafts acylation reaction

Two kinds of macrocyclic arylene ketone oligomers have been synthesized in high yield from phthaloyl dichloride and various bridge-linking electron-rich aromatic hydrocarbons via the modified Friedel-Crafts acylation reaction. The presence of a Lewis base in this reaction is demonstrated to be advantageous for forming macrocycle oligomers. These resultant oligomers can undergo melt ring-opening polymerization to give polymers with high T. and excellent thermal stability.

Liquid-liquid extraction of cerium(IV) from nitric acid media by di-(2-ethylhexyl) 2-ethylhexyl phosphonate (DEHEHP)

In this paper, the extraction of Ce(IV) from nitric acid solutions is investigated using di-(2-ethylhexyl) 2-ethylhexyl phosphonate (DEHEHP, B) in heptane as extractant. Ce(IV) can be extracted effectively from nitric acid solution, whereas it is poorly extracted from sulfuric acid solution. Compared with some other organophosphorus esters, DEHEHP has moderate extractablity for Ce(IV). The extraction efficiency varies with diluent in the order: aliphatic hydrocarbons > nitrobenzene > aromatic hydrocarbons > carbon tetrachloride > chloroform. Regeneration and loading capacities of DEHEHP have also been examined. Ce(IV) extraction in HNO3 solutions as well as extraction of HNO3 and H2O have been systematically studied. The Ce(IV) extraction increases with an increasing of HNO3 concentration and exhibits the maximum distribution ratio at 1-1.5 mol/L HNO3. Nitric acid, as a source of nitrate ion, enhances the extraction of metal ion. But it also competes with metal ions for extractant molecules by its own extraction under high acidities. The proposed extraction process is described by the following equilibrium equations

Improved thermal fractionation technique for chain structure analysis of ethylene/alpha-olefin copolymers

In this report, we describe an improved thermal fractionation technique used to characterize the polydispersity of crystalline ethylene sequence length (CESL) of ethylene/alpha -olefin copolymers. After stepwise isothermal crystallization, the crystalline ethylene sequences are sorted into groups by their lengths. The CESLs are estimated using melting points of known hydrocarbons. The content of each group is determined using the calibrated peak area. The statistical terms: the arithmetic mean (L) over bar (n), the weighted mean (L) over bar (w) and the broadness index I = (L) over bar (w)/(L) over bar (n) are used to describe the distribution of CESL. Results show that improved thermal fractionation technique can quantitatively characterize the polydispersity of CESL with a high degree of accuracy.

Effects of zeolites on the pyrolysis of polypropylene

With the intention of understanding chemical recycling of waste polymers, various kinds of zeolites were used as catalysts in the pyrolysis of polypropylene (PP). The effects of zeolites on the degradation temperature and pyrolyzed products of PP were studied. It was found that the degradation temperature of PP strongly depended on the type of zeolite used and the amount added. One type of HY zeolite (320HOA) was shown to be a very effective catalyst. Pyrolysis products, which were identified by using a coupled gas-chromatograph-mass-spectrometer, were also affected by the addition of zeolites. Some zeolites did not change the structure of the products but narrowed the product distribution to a smaller molecule region, while the HY zeolite led to hydrocarbons concentrated at those containing 4-9 carbons. Furthermore, some new compounds with cyclic structures were found in the presence of the HY zeolite. (C) 1996 Elsevier Science Limited

CORRELATION-ANALYSIS IN STRUCTURE AND CHROMATOGRAPHIC DATA OF ORGANOPHOSPHORUS COMPOUNDS BY GAI

This approach is undertaken to examine the correlation ability of the general a(N)-index (GAI) to predict chromatographic behavior. The test is performed on various types of organophosphorus compounds. The results demonstrate that the GAI possesses a good correlation with chromatographic properties.

Seismic characteristics of a reef carbonate reservoir and implications for hydrocarbon exploration in deepwater of the Qiongdongnan Basin, northern South China Sea

Our analysis of approximately 40,000 km of multichannel 2-D seismic data, reef oil-field seismic data, and data from several boreholes led to the identification of two areas of reef carbonate reservoirs in deepwater areas (water depth >= 500 in) of the Qiongdongnan Basin (QDNB), northern South China Sea. High-resolution sequence stratigraphic analysis revealed that the transgressive and highstand system tracts of the mid-Miocene Meishan Formation in the Beijiao and Ledong-Lingshui Depressions developed reef carbonates. The seismic features of the reef carbonates in these two areas include chaotic bedding, intermittent internal reflections, chaotic or blank reflections, mounded reflections, and apparent amplitude anomalies, similar to the seismic characteristics of the LH11-1 reef reservoir in the Dongsha Uplift and Island Reef of the Salawati Basin, Indonesia, which house large oil fields. The impedance values of reefs in the Beijiao and Ledong-Lingshui Depressions are 8000-9000 g/cc x m/s. Impedance sections reveal that the impedance of the LH11-1 reef reservoir in the northern South China Sea is 800010000 g/cc x m/s, whereas that of pure limestone in BD23-1-1 is > 10000 g/cc x m/s. The mid-Miocene paleogeography of the Beijiao Depression was dominated by offshore and neritic environments, with only part of the southern Beijiao uplift emergent at that time. The input of terrigenous sediments was relatively minor in this area, meaning that terrigenous source areas were insignificant in terms of the Beijiao Depression: reef carbonates were probably widely distributed throughout the depression, as with the Ledong-Lingshui Depression. The combined geological and geophysical data indicate that shelf margin atolls were well developed in the Beijiao Depression, as in the Ledong-Lingshui Depression where small-scale patch or pinnacle reefs developed. These reef carbonates are promising reservoirs, representing important targets for deepwater hydrocarbon exploration. (C) 2008 Elsevier Ltd. All rights reserved.

海带对多环芳烃的吸收及代谢研究

多环芳烃是环境中一种普遍存在的有机污染物。目前国内水体已受到了多环芳烃的严重污染，因而研究开发治理有机污染物的有效方法对于沿海生态系统的恢复具有重要意义。但现在对水体尤其是海洋环境中的多环芳烃植物修复仍知之甚少。 本课题在实验室中研究了海带对两种多环芳烃（菲和芘）不同浓度下的吸收及降解，并对代谢过程进行了初步探索。海带对多环芳烃的吸收及代谢与多环芳烃的初始浓度及种类有关。 多环芳烃浓度较低（<0.2mg/l）时，海带对多环芳烃具有很强的吸收及代谢能力。0.1mg/l多环芳烃中，加入海带后对菲和芘的去除效率分别为：99.88-99.89%和94-96.5%；而不加海带的对照液中菲和芘的去除效率分别为46.9%和44.7%。有约51.34%的菲、45.7%的芘被海带完全去除，证实了海带对多环芳烃的代谢。检测到了海带对芘的代谢产物二氢二醇芘，说明海带对多环芳烃的代谢过程为双加氧酶催化；且有少量二氢二醇芘的配合物生成，但结合物结构尚不确定。 高浓度的多环芳烃对海带具有极大危害，强烈抑制了海带生长，破坏了其色素体。海带体内的叶绿素-a及类胡萝卜素含量随时间、多环芳烃浓度而下降；过氧化物酶（POD）及超氧化物歧化酶（SOD）受激后活性升高，能对植物的生长起到一定的保护作用； POD能参与到藻体对多环芳烃的第一步氧化过程。 总之，海带能在一定浓度范围内（低于0.2mg/l）吸收、降解多环芳烃，能用来对多环芳烃污染海域进行植物修复。研究也表明高浓度的多环芳烃对海带的生长有强烈抑制作用。将来还应对海带对多环芳烃的具体代谢路径，以及代谢产物的生态影响进行进一步的研究。

中国近海沉积物中黑碳和多环芳烃的研究

黑碳和多环芳烃都是燃烧产生的污染物，并广泛存在于土壤及海洋特别是近海沉积物中。由于黑碳和多环芳烃对环境及生态系统具有不同的影响途径和危害，多年来一直受到环境研究者的极大重视。本文对我国近海几个海区（渤海湾、北黄海、胶州湾、南海珠江口及其邻近海区）沉积物中黑碳和多环芳烃的含量、分布及来源进行了研究，并首次对各海区表层沉积物中黑碳和多环芳烃的相关性进行了分析。 数据显示，中国近海各海区（渤海湾、北黄海、胶州湾、南海珠江口及其邻近海区）表层沉积物中黑碳的浓度范围为0.1 - 2.45 mg/gdw，占总有机碳浓度的1 - 41%，具有较大的空间差异。渤海湾表层沉积物中黑碳浓度最高（平均为2.18 mg/gdw），占沉积物中总有机碳浓度的27 - 41%。相比之下，北黄海、胶州湾和南海珠江口及其邻近海区表层沉积物中黑碳浓度较低，分别占沉积物中总有机碳浓度的6%、8%和5%。黑碳的分布主要受其来源的影响，陆地来源和河流输入是中国近岸海区表层沉积物中黑碳的重要来源。该研究显示黑碳在沉积物中的埋藏可能代表我国近海各海区碳循环中的一个重要碳汇。 中国近海各海区（渤海湾、北黄海、南海珠江口及其邻近海区）表层沉积物中多环芳烃的浓度范围为47.5 – 3673.5 ng/g（均为干重），亦具有很大的空间差异。渤海湾中多环芳烃的浓度最高（82.9 – 3673.5 ng/g），反映了该地区受人类污染严重的特征。在三个海区表层沉积物中，单组分多环芳烃的分布也具有明显不同的特征，渤海湾主要以5、6环的多环芳烃为主，而北黄海和南海珠江口及其邻近海区3、4环多环芳烃的浓度较高。基于多环芳烃的单组分分布特征和一些特殊指数，可以得到渤海湾表层沉积物中的多环芳烃以木材、煤的不完全燃烧来源为主，而北黄海海区和南海珠江口及其邻近海区的多环芳烃显示出木材、煤的燃烧和石油燃烧的混合来源。 中国近海表层沉积物中黑碳浓度与多环芳烃的浓度并不存在很好的相关性，这说明中国近海表层沉积物中的黑碳和多环芳烃具有不同的来源，且在沉积物中的埋藏受控于不同的地球化学作用。

Triterpane and sterane biomarkers in the YA13-1 condensates from Qiongdongnan Basin, South China Sea

Triterpanes and steranes in condensates from the YA13-1 gas field, Qiongdongnan Basin, were monitored. The YA13-1 condensates have unusual biomarker distributions dominated by terpanes and steranes derived from higher plants. Anomalously abundant 1 got-oleanane and remarkably abundant bicadinanes are present in the YA13-1 condensates, whereas the 17alpha-hopane contents are extremely low. Taraxastane and significantly abundant 17alpha-diahopanes occur in the condensates. In addition, a number of unknown C-29 and C-30 pentacyclic triterpanes including previously unreported compounds were detected in the condensates, some of which are significantly abundant. The unknown compounds may be terrestrial biomarkers. C-29 homologues are relatively predominant among the regular and rearranged steranes. The diasterane concentrations are markedly higher than those of regular steranes. The maturity of the YA13-1 condensates is relatively high, at the peak to late oil generation stage (corresponding to 0.85-1.10% Ro), based on sterane and terpane and including bicadinane maturity parameters (i.e. T/(T-1 + R) and 2T/R bicadinane ratios). The above maturity assessment result is different from that based on diamondoid maturity parameters (%Ro = 1.60-1.70) [Org. Geochem. 25 (1996) 179], which can be explained by a contribution of hydrocarbons from two sources at different depths. The YA13-1 condensates were probably generated from the Yacheng and Lingshui coal-bearing source rocks buried both in the Qiongdongnan Basin (3400-5000 m) and in the Yinggehai Basin (>5000 m). The possible contribution of lower maturity hydrocarbons from the Yacheng and Lingshui Formations (3400-4100 m) in the Qiongdongnan Basin to the YA13-1 gases and condensates should not be neglected. (C) 2003 Elsevier Science B.V. All rights reserved.

Organic geochemical studies of sinking particulate material in China sea area(I) - Organic matter fluxes and distributional features of hydrocarbon compounds and fatty acids

Sinking particulate material collected from Nansha Yongshu reef lagoon and the continental shelf of the East China Sea by sediment traps has been analyzed and studied for the first time using organic geochemical method. The results show that about half of the sinking particulate organic matter in the two study areas are consumed before reaching the depth of 5 m to the sea floor and the degree of this consumption in Yongshu reef lagoon is larger than that in the continental shelf of the East China Sea. The distributions of hydrocarbons and fatty acids indicate that the minor difference of biological sources of sinking particulate organic matter exists between Yongshu reel lagoon and the continental shelf of the East China Sea, but they mainly come from marine plankton. Stronger biological and biochemical transformations of sinking particulate organic matter are also observed and the intensity of this transformation in Yongshu reef lagoon is greater than that in the continental shelf of the East China Sea. It is found that the occurrence of C-25 highly branched isoprenoid (HBI) diene may be related to the composition of diatom species.

Cadinane Sesquiterpenes from the brown alga Dictyopteris divaricata

Seven new cadinane sesquiterpenes, (-)-(1R,6S,7S,10R)-1-hydroxycadinan-3-en-5-one (1), (+)-(1R,5S,6R,7S, 10R)-cadinan-3-ene-1,5-diol (2), (+)-(1R,5R,6R,7S,10R)-cadinan-3-ene-1,5-diol (3), (+)-(1R,5S,6R,7S,10R)-cadinan-4(11)-ene-1,5-diol (4), (+)-(1R,5R,6R,7R,10R)-cadinan-4(11)-ene-1,5,12-triol (5), (-)-(1R,4R,5S,6R,7S, 10R)-cadinan-1,4,5-triol (6), and (-)-(1R,6R,7S,10R)-11-oxocadinan-4-en-1-ol (7), together with nine known compounds were isolated from the brown alga Dictyopteris divaricata. The structures of the new natural products, as well as their absolute configuration, were established by means of spectroscopic data including IR, HRMS, 1D and 2D NMR, single-crystal X-ray diffraction, and CD. All compounds were inactive against several human cancer cell lines including lung adenocarcinoma (A549), stomach cancer (BGC-823), breast cancer (MCF-7), hepatoma (Bel7402), and colon cancer (HCT-8) cell lines.

Minor sesquiterpenes with new carbon skeletons from the brown alga Dictyopteris divaricata

Five minor sesquiterpenes (1-5) with two novel carbon skeletons, together with a minor new oplopane sesquiterpene ( 6), have been isolated from the brown alga Dictyopteris divaricata. By means of spectroscopic data including IR, HRMS, 1D and 2D NMR, and CD, their structures including absolute configurations were assigned as (+)-(1R, 5S, 6S, 9R)3- acetyl-1-hydroxy-6-isopropyl-9-methylbicyclo[4.3.0] non-3-ene ( 1), (+)-(1R, 3S, 4S, 5R, 6S, 9R)-3-acetyl-1,4-dihydroxy-6- isopropyl-9-methylbicyclo[4.3.0] nonane (2), (+)-(1R, 3R, 4R, 5R, 6S, 9R)-3-acetyl-1,4-dihydroxy-6-isopropyl-9-methylbicyclo[ ;4.3.0] nonane ( 3), (+)-(1S, 2R, 6S, 9R)-1-hydroxy-2-(1-hydroxyethyl)-6-isopropyl-9-methylbicyclo[4.3.0] non-4-en-3-one (4), (-)-( 5S, 6R, 9S)-2-acetyl-5-hydroxy-6-isopropyl-9-methylbicyclo[4.3.0] non-1-en-3-one ( 5), and (-)-( 1S, 6S, 9R)- 4-acetyl- 1-hydroxy-6-isopropyl-9-methylbicyclo[ 4.3.0] non-4-en-3-one ( 6). Biogenetically, the carbon skeletons of 1-6 may be derived from the co-occurring cadinane skeleton by different ring contraction rearrangements. Compounds 1-6 were inactive (IC50 > 10 mu g/mL) against several human cancer cell lines.

Norsesquiterpenes from the brown alga Dictyopteris divaricata

Three bisnorsesquiterpenes (1-3) with novel carbon skeletons and a norsesquiterpene (4) have been isolated from the brown alga Dictyopteris divaricata. By means of spectroscopic data including IR, HRMS, 1D and 2D NMR techniques, single-crystal X-ray diffraction, and CD, their structures including absolute configurations were proposed as (+)-1R,6S,9R)-1-hydroxyl-6-isopropyl-9-methylbicyclo[4.3.0]non-4-en3-one (1), (-)-(1S,6S,9R)-1-hydroxyl-6-isopropyl-9-methylbicyclo[4.3.0] non-4-en-3-one (2), (+)-(5S,6R,9S)5-hydroxyl-6-isopropyl-9-methylbicyclo [4.3.01 non-1-en-3-one (3), and (-)-(1R,7S,10R)-1-hydroxy-1lnorcadinan-5-en-4-one (4). Biogenetically, the carbon skeleton of 1-3 may be derived from the co-occurring cadinane skeleton by ring contraction and loss of two carbon units, and compound 4 from the oxidation of cadinane derivatives. Compounds 1-4 were inactive (IC50 > 10 mu g/mL) against several human cancer cell lines including lung adenocarcinoma (A549), stomach cancer (BGC-823), breast cancer (MCF-7), hepatoma (Bel7402), and colon cancer (HCT-8) cell lines.