ALIPHATIC C-H BOND RESPONSES IN THE 900-700 cm-1 REGION OF THE FTIR SPECTRA OF COAL TARS

Four bituminous coals were comprehensively separated by column chromatography into a number of fractions. Four aromatic hydrocarbon fractions of each tar were analyzed by FTIR spectroscopy, and the 900-700 cm^-1 spectral region was evaluated. This spectral region was found to be composed of at least 14 separate bands, which were resolved by using self-deconvolution and curve-fitting procedures. The bands near 821 cm^-1, 791 cm^-1, and 784 cm^-1 were proposed to originate from rocking vibrations of aliphatic C-H bonds. For the tar samples with a proton aromaticity between 0.21 and 0.37, these bands account for on average 12% of the total integral intensity of the 900-700 cm^-1 region. This percentage cannot likely be neglected in a correct quantitative evaluation of the region and calculation of the aromatic hydrogen concentration. However, a correct resolution of the bands can be very difficult in the FTIR spectra of a complex material, such as coal.     

煤中的惰性组分与煤成油

通过对世界上煤成油田与其煤岩显微组分的对比研究后发现，许多煤成油田出现在煤中惰性给分含量较高的地区。笔者结合对煤中惰性组的物性分析，认为与镜质组相比，惰性组具有较小的吸附性和较大孔隙直径，它为煤中形成烃类的富集和运移提供了较好的条件。煤中具较高生烃能力的富氢组分与大量惰性组的配合，对煤成油的富集和运移有促进作用。     

HYDRATION OF BUTENE-1 OVER H.-MORDENITE AND H-MORDENTTE COMPOSITED WITH ZEOLITE-β

The hydration of butene-1 over H-mordenite and H-mordenite composited with different amounts of zeolite-β has been investigated in a batch reactor. The products of the reaction were sec-butanol (SBA), diisobutylether (DIBE) and C₈-oligmer. The reaction was carried out over H-mordenite at different operational conditions of a reaction temperature and built-up pressure. The maximum activity (46% of the thermodynamic equilibrium) of H-mordenhe was observed at 250°C and 180.27 atm with 88% selectivity of SBA and no formation of C« dimmer by-product. The structural characteristics of a H-form of the composited catalysts, containing 10, 15 and 45 wt% of zeolite-β, were studied by means of an electron dispersion system (EDS) technique in order to determine SiO₂/Al₂O₃ ratio and % degree of exchange. It was found that SiO₂/Al₂O₃ ratio ranges between 20.2 and 29.61 indicating that all the catalysts could be considered as siliceous zeolites. The acidic properties of the pure mordenites and those composited with zeolite-β were determined potentiometrically in an aqueous medium. From the results obtained, it is obvious that the catalysts, containing mordenite composited with 15 and 45 wt% of zeolite-β, possess stronger acidic -OH's than pure mordenites. Also, the hydration activity of zeolites seemed to be strongly correlated with their protonic acid strength. The activity and selectivity of the composited zeolites for the hydration reaction were studied at the optimum operational conditions and compared with those of pure mordenite. The binary composited zeolites, containing 15 and 45 wt% of zeolite-β were found to be more active and selective for the hydration of butene -1 than those of pure mordenite. It was suggested that the activity and selectivity of the binary zeolite catalyst system may be due to shape selectivity of β-zeolite, high surface acidity and hydrophobic nature exhibited by the two forms of zeolites.     

用S—甲基化反应和^2H NMR,^13C NMR表征石油中有机硫的结构

提出用衍生物－ＮＭＲ表征石油中的有机硫结构的方法，在四氟硼酸银的存在下，分别用＾２Ｈ或＾１３Ｃ同位素富集的碘甲烷，把石油中的有机硫定量地转变为相应的甲基镀盐，然后用＾２ＨＮＭＲ和＾１３ＣＮＭＲ表征硫化物的结构，给出了一些模型甲工铳盐的＾２ＨＮＭＲ和＾１３ＣＮＭＲ化学位移值。分析结果表明，石油中噻吩类为苯并噻吩型等结构，硫醚为脂肪硫醚，二苯硫醚及α－萘基甲基硫醚等，阿拉伯原油样品中，大约７０％的硫化     

THE INFLUENCE OF PARTICLE SIZE ON THE PERFORMANCE OF γ-RAY DENSITY METERS

This report presents results obtained from an experimental investigation on the effect of the size of coal particles on γ-ray density meter accuracy. The experimental set up used consisted of a γ-ray density meter, a stirrer and Hewlett Packard data acquisition system. Results obtained for particle size ranges 100 × 140 and 60 × 100 at 1%, 3%, 10%, 15% and 20% solids by weight, showed that meter response is strongly dependent on the size of the coal particles.     

NMR ANALYSIS OF AMBER IN THE ZUBAIR FORMATION,KHAFJI OILFIELD (SAUDI ARABIA – KUWAIT): COAL AS AN OIL SOURCE ROCK?

Amber samples obtained from coal deposits in the Zubair Formation at a depth of 1,800 m from the offshore Khafji oilfield (Saudi Arabia - Kuwait Partitioned Neutral Zone) were subjected to NMR analysis. The resulting spectra identified the samples as originating from trees belonging to the genus Agathis. The NMR spectra were virtually identical to those obtained from Lower Cretaceous amber from Lebanon, Israel and Jordan, suggesting that a large forest of Agathis levantensis extended across the Arabian Plateau from the Levant to the Gulf. In this case, the forest would have extended a distance of approximately 1500 km, which would make it the largest amber-producing forest known. It is suggested that the oil in the Khafji and adjoining Safaniya oilfields could have been derived from coal produced, at least in part, by Agathis levantensis.     

琼东南盆地崖南凹陷崖13-1构造与崖21-1构造成藏条件比较

琼东南盆地崖南凹陷西缘发育有我国最大的海上气田―― YA1 3 -1气田。而位于同一凹陷东南缘的 YA2 1 -1构造的天然气成藏条件欠佳 ,近年在该构造所钻探的几口井均未获得突破。从烃源条件、储层条件和能量场配置等 3个方面探讨了无突破的原因。 YA1 3 -1气田天然气主要来自于琼东南盆地的崖南凹陷 ,且可能有莺歌海盆地埋深分别大于 445 0 m和 470 0 m的崖城和陵水组烃源岩的贡献。YA2 1 -1构造的主要源岩可能为乐东凹陷 ,其浅海 A型源岩和浅海 B型源岩的发育条件均很差。据沉积相的研究 ,YA2 1 -1构造的陵水组为滨海相沉积 ,相对于 YA1 3 -1气田储层来说 ,粒度变细 ,且以细砂岩为主。YA1 3 -1构造和 YA2 1 -1构造的能量场配置和流体活动也有明显的不同。YA1 3 -1构造盖层发育超压 ,储层为常压并为侧向流体充注体系 ,属于所谓的“黄金配置”能量场。而 YA2 1 -1构造储层和盖层均发育超压 ,且盖层被压裂 ,属垂向流体泄放体系。总之 ,YA2 1 -1构造具有烃源条件差、储层条件差、区域能量配置条件差“三差”特点 ,故难以形成大气田     

CHARACTERIZATION OF DISSOLUTION PRODUCTS FROM TWO TURKISH LIGNITES BY 1 H NMR, IR AND GC TECHNIQUES

Some structural features of the dissolution products from two Turkish lignites ( Beypazari and Tuncbi-lek lignites) have been investigated with proton nuclear magnetic resonance and infra-red spectroscopies and gas chromatography. The results indicate that, in general, no substantial changes occur in the structural characteristics of the soluble products obtained from different extraction conditions. This is true especially for preasphaltene and asphaltene fractions. On the other hand, some structural differences were observed in the compositions of oil fractions especially in the neutral fraction of oils from the different experimental conditions. The neutral oils from the low temperature and short time extractions are mainly consisted of alkylated aromatics and include a very small quantity of longer chain paraffins. Whereas the oils from the extractions at high temperatures and longer times include several long straight-chain paraffins (C15 - C32) with higher quantity. Hydrogen atmosphere is moderately effective for deoxygenation of the products. Dealkylation reactions for smaller molecules are insignificant but hydrogen atmosphere is relatively effective for the dealkylation of larger molecules. Higher temperature and longer extraction period accelerate the liquid phase pyrolysis.     

1H→13C和1H→29Si CP/MAS NMR研究钛硅分子筛晶化

采用1H→13C CP／MAS NMR跟踪研究了模板剂TPAOH在晶化过程中的作用。结果表明，在晶化初期，TPA 以吸附带有负电荷的硅钛胶聚合体为主，硅钛相互作用逐渐形成微小晶核，这种微小晶核缓慢长大进而形成分子筛；用1H→29Si CP／MAS NMR增强钛硅分子筛晶化过程中29Si分辩信号，效果显著。在钛与硅氧作用形成具有复杂结构的微小晶核时，钛对硅的影响作用较小；当微小晶核突发形成分子筛时，钛进入分子筛骨架，对硅的影响作用显著增大。初步探讨了钛硅分子晶化生成分子筛的晶化机理。     

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根据川中一川南过渡带雷一＾１亚段在地史发展中的实际情况，一是采用压实数值模拟方法，重建雷一＾１亚段的埋藏史，二是用古水动力场数值模拟方法，恢复雷一＾１段的含水层在各时期的古水动力场，并以此为基础研究古体势场和古构造演化之间的搭配关系，揭示了区内雷一＾１亚段在地史中天然气的运聚规律。研究结果表明，区内雷一＾１亚段在 地史发展中一直处于泸州古隆起北斜坡的低水势区，是地下水汇集的过流带，燕山期形成的安岳     

COMPARATIVE REACTION STUDY OF METHYLCYCLOHEXANE AND 3-METHYLHEXANE IN H2 AND N2 ON Pt/Al2O3 CATALYST

ABSTRACT

The reaction of methylcyclohexane and 3-methylhexane were studied in a pulse microcatalytic reactor using H₂ and N₂ carriers on Pt/Al₂O₃ catalyst at temperatures from 350 to 500°C, contact times (W/F) of 1.25 × 10^?3–3.75 × 10^?3 g min/ml and a total pressure of 4.0 kg/cm². In N₂, there was complete conversion of methylcyclohexane to methane, benzene and toluene while similar products were produced for 3-methylhexane, albeit with diminished conversion level. In H₂, methane was produced from 3-methylhexane conversion while aromatization without demethylation was obtained in addition to some cracking for methylcyclohexane at the low temperature range (350–400°C); a higher temperature range (460–500°C) resulted in complete fragmentation for methylcyclohexane. In H₂–N₂ mixtures, the presence of N₂ of not less than 50% in the carrier gas stream yielded an aromatic catalyst at conditions where only cracking activity was previously evident. The differences in product distribution and/or product types for the two reactants in H₂ and N₂ suggest a different reaction mechanism for both reactants.     

COMPARATIVE REACTION STUDY OF METHYLCYCLOHEXANE AND 3-METHYLHEXANE IN H2 AND N2 ON Pt/Al2O3 CATALYST

The reaction of methylcyclohexane and 3-methylhexane were studied in a pulse microcatalytic reactor using H₂ and N₂ carriers on Pt/Al₂O₃ catalyst at temperatures from 350 to 500°C, contact times (W/F) of 1.25 × 10^-3-3.75 × 10^-3 g min/ml and a total pressure of 4.0 kg/cm². In N₂, there was complete conversion of methylcyclohexane to methane, benzene and toluene while similar products were produced for 3-methylhexane, albeit with diminished conversion level. In H₂, methane was produced from 3-methylhexane conversion while aromatization without demethylation was obtained in addition to some cracking for methylcyclohexane at the low temperature range (350-400°C); a higher temperature range (460-500°C) resulted in complete fragmentation for methylcyclohexane. In H₂-N₂ mixtures, the presence of N₂ of not less than 50% in the carrier gas stream yielded an aromatic catalyst at conditions where only cracking activity was previously evident. The differences in product distribution and/or product types for the two reactants in H₂ and N₂ suggest a different reaction mechanism for both reactants.     

微米TS-1的水热改性及其丁酮氨氧化性能

 采用水热改性对微米TS-1进行处理, 考察了改性温度、改性时间及水的用量等对其在丁酮氨氧化反应中催化性能的影响. 采用TEM、SEM、UV-Vis、XRD、IR及N₂物理吸附等手段,对水热改性前后的样品进行了表征. 结果表明, 水热改性对微米TS-1分子筛的骨架结构影响不大,但会使孔分布、吸附曲线等有所变化, 水热改性后的微米TS-1在丁酮氨氧化反应中的催化性能明显改善. 水热处理的最佳条件是: 每100g的微米TS-1用水30mol, 改性温度170℃, 改性时间48h.     

水处理药剂阻CaCO3垢性能与循环水中[Ca^2＋]和[HCO3—]的关系

考察了水处理药剂在不同[Ca2 ]、[HCO]水质条件下阻CaCO3垢的一些规律。结果表明，同一种药剂阻CaCO3垢性能不仅受水中[Ca2 ] ［HCO］总值的影响，还与[Ca2 ]／[HCOF]有关。采用透射电镜对不同试验条件下垢样观察分析，发现水处理剂对不同条件下生成的CSCO3垢样表现出不同的扭曲作用，从而影响水处理剂的阻CaCO3垢性能。     

含次膦酸基-羧基-磺基的共聚物合成工艺优化及其特性粘数与阻垢性能关系的研究

以过硫酸钠为引发剂,次磷酸钠为链终止剂,丙烯酸(AA)和2-丙烯酰胺基-2-甲基丙磺酸(AMPS)为单体合成了含次膦酸基、羧基和磺基于一体的共聚物。测试了该共聚物的特性粘数[η],并讨论了[η]与阻垢性能的关系。结果表明,[η]=8.0~20.0 dL／g时,该聚合物阻钙垢性能最佳可达96%~98%。共聚物的最佳合成工艺条件是:AA／AMPS／过硫酸钠／次磷酸钠(摩尔比)=0.4:0.03:0.03:0.02,反应温度70℃,滴加时间1 h,反应时间2 h。     

塔中45 井泥盆纪鱼类化石的发现及“东河砂岩”的时代

1990 年在东河1井发现了“东河砂岩”,1993年又在草湖地区草2井找到胴甲鱼化石。经过近几年的古生物地层学的研究, 人们先后找到了石炭-泥盆系界线附近的牙形石、孢粉化石, 从而将“东河砂岩” 划归泥盆系, 被大家所接受。近期,在塔中45 井发现泥盆纪鱼类化石, 使得塔中地区“东河砂岩”划归泥盆系有了更充分的证据。     

CZ3—1E气／液相双效缓蚀剂的研制与应用

在原来复合使用的液相缓蚀剂ＣＺ３１ ＋ 气相缓蚀剂ＣＺ３３ 的基础上研制出一种改进的气、液相双效缓蚀剂ＣＺ３１Ｅ。该剂不仅保持原缓蚀剂缓蚀率高、用量少等特点,而且克服了原缓蚀剂有一定异味、加注不便、成本费用高的缺点。在室内评价中,在未作预膜处理、Ｈ２Ｓ分压１ ．２ ＭＰａ、ＣＯ２ 分压２．８ ＭＰａ、温度８０ ±２℃、静态、腐蚀时间７２ ｈ 条件下,以加入ＣＺ３１Ｅ缓蚀剂１０００ ｐｐｍ 的脱氧磨溪气田地层水为腐蚀介质,ＮＴ８０ＳＳ钢试片的气相腐蚀速率为０．０４９５ ｍ ｍ／ａ,缓蚀率９１．２％ ,液相腐蚀速率为０ ．０６４３ ｍ ｍ／ａ,缓蚀率９０．５ ％ ,测试后试片光亮,未见点蚀。对磨溪气田使用过的数种缓蚀剂进行全面对比,表明ＣＺ３１Ｅ 各项性能均较佳,可满足含硫气田气、液相防腐的需要。     

H2O影响γ-Al2O3吸附SO2、NO的机理分析

利用分子模拟和实验探究结合，考察了H2O影响γ-Al2O3吸附SO2、NO的机理。在构造γ-Al2O3(110C)面基础模型和建立H2O，SO2，NO等吸附质分子在(110C)面的吸附模型后，确定了优化的吸附构象。通过电荷密度和分波态密度分析发现，吸附质与(110C)面Al位点存在明显的电子转移，进而形成稳定的吸附结构。H2O通过分子吸附和解离吸附，占据Al3c和O3c位点；SO2主要吸附在Al3c、Al4c位点；NO与Al4c位点相互作用，需要在O3c位点氧化。因此，H2O与SO2和NO在γ-Al2O3(110C)面的Al3c和O3c位点存在竞争吸附。试验结果与分子模拟理论分析结果基本一致，H2O不利于SO2和NO在γ-Al2O3上的吸附。     

H2O影响γ-Al2O3吸附SO2、NO的机理分析

利用分子模拟和实验探究结合,考察了H2O影响γ-Al2O3吸附SO2、NO的机理。在构造γ-Al2O3(110C)面基础模型和建立H2O,SO2,NO等吸附质分子在(110C)面的吸附模型后,确定了优化的吸附构象。通过电荷密度和分波态密度分析发现,吸附质与(110C)面Al位点存在明显的电子转移,进而形成稳定的吸附结构。H2O通过分子吸附和解离吸附,占据Al3c和O3c位点;SO2主要吸附在Al3c、Al4c位点;NO与Al4c位点相互作用,需要在O3c位点氧化。因此,H2O与SO2和NO在γ-Al2O3(110C)面的Al3c和O3c位点存在竞争吸附。试验结果与分子模拟理论分析结果基本一致,H2O不利于SO2和NO在γ-Al2O3上的吸附。     

乌尔逊凹陷南二段与大二段油气成藏条件差异性分析

通过乌尔逊凹陷南二段与大二段油气成藏条件及其差异性分析得到，乌尔逊凹陷南二段在源岩条件、盖层条件、盖源时空匹配关系、断源时空匹配关系和油气运移形式上与大二段均存在着差异。前者明显好于后者，表明乌尔逊凹陷南二段油气成藏条件明显优于其大二段，这是造成目前乌尔逊凹陷南二段油气显示明显好于大二段的根本原因。