Evaluation of the aromatic structure of coal tar pitch by solid and solution state n.m.r.

Rapid magic angle spinning has been used to obtain sideband-free high field ¹³C n.m.r. spectra of coal tar pitches in the solid state. However, the unfavourable cross-polarization and ¹H relaxation characteristics make it difficult to accurately estimate concentrations of quaternary aromatic carbon using the dipolar dephasing method. The concentrations of bridgehead aromatic carbon in the whole pitch and toluene-insoluble fraction investigated were deduced using a combination of solid and solution state n.m.r. and elemental analyses.     

Two-dimensional n.m.r. characterization of cycloaliphatic epoxy resins

The cycloaliphatic epoxy resins were studied by various two-dimensional nuclear magnetic resonance (2D n.m.r.) spectroscopies. The ¹³C n.m.r. spectra of the epoxy resins were assigned by using DEPT and 2D INADEQUATE techniques and the ¹H n.m.r. spectra were assigned by using 2D ¹H---¹H and ¹H---¹³C COSY techniques. Complete characterization of the samples synthesized by the oxidation of cyclohexene derivatives not only revealed the existence of the stereochemical isomers resulting from the structural difference of the oxide rings in the samples but also provided the composition ratio of the isomers.     

宁东红石湾煤大分子模型构建及量子化学计算

使用工业分析、元素分析、固体核磁（¹³C NMR）、X射线光电子能谱（XPS）、傅里叶变换红外光谱（FT-IR）对宁东红石湾（HSW）煤样进行表征,获得煤样中元素赋存的种类、价态、化学键环境等物质微观结构的关键参数。结果表明HSW煤结构以芳香族为主,占75.96%,桥接芳碳与周碳比为0.315,可知其结构中以萘为主,苯和蒽为辅。氧原子主要以醚氧基（C-O）、羰基（C=O）和羧基（-COO）的形式存在,其中C-O占53.57%。氮原子以吡啶和吡咯的形式存在。苯环的连接方式以三、四取代为主,分别占47.77%、32.97%,脂肪族中环烷烃或脂肪烃-CH₃占优势。确定HSW煤的分子式为C₂₂₁H₁₄₈O₂₈N₂,分子量为3142.32。在此基础上结合计算机辅助实现了二维和三维大分子模型构筑。应用量子化学计算对HSW煤大分子模型进行了优化及核磁共振、红外光谱模拟,验证了所建模型的合理性。最终实现了HSW煤的微观分子结构的实验与量子化学描述。     

Evaluation of a delayed coking process by H and C n.m.r. spectroscopy: 1. Material balances

The use of ¹H and ¹³C nuclear magnetic resonance (n.m.r.) spectroscopy to evaluate the performance of a delayed coking process is presented in a series of papers, of which this is the first. A meaningful analysis requires an accurate balance, which in turn requires analysis of the various types of atoms in the feed and in all products, including solid coke, as well as the amounts of each. Product yields were determined in a delayed coking pilot plant. Complete n.m.r. (¹H and ¹³C) characterization of feed and all delayed coking products, using a consistent classification, was combined with pilot plant data to obtain the total distribution of carbon and proton atoms in the delayed coking process. Changes in carbon and hydrogen distributions (products versus feedstock) reveal the nature of the thermal cracking reactions involved; the main change is a substantial increase in the number of aromatic and paraffinic carbons at the expense of naphthenic carbons.     

High resolution solid state C n.m.r. of Canadian peats

Peat samples from three locations in Quebec, Canada, were characterized by ¹³C CP/MAS n.m.r. spectroscopy. The n.m.r. analysis indicates that the peats contain a significant amount of unaltered plant components including cellulose, hemicellulose, lignin, waxes and resins. Integration of specific regions of the spectra can give semi-quantitative estimates of some of these plant components and, in limited cases, information about the degree of decomposition can be obtained from the ¹³C CP/MAS n.m.r. spectrum. Dipolar dephasing experiments and difference spectroscopy were found to be valuable techniques for spectra assignments and enhancement of compositional differences.     

Structural analysis of Aleksinac oil shale kerogen by high-resolution solid-state C n.m.r. spectroscopy

A sample of kerogen from Aleksinac oil shale was examined by high-resolution solid-state ¹³C n.m.r. spectroscopy. The presence and relative proportions of kerogen structural units were estimated using a combination of NQS and T_1C methods with a peak-synthesis technique applied to the ¹³C CP—MAS spectrum. Relaxation parameters from these experiments were used to estimate differences in relative ‘mobility’ of various structural units. The kerogen was found to be highly aliphatic and to contain 79% long-chain aliphatic plus alicyclic structures, as well as 9% aromatic structures. These findings are in good agreement with the characterization of the same kerogen from its oxidation products.     

Dielectric and C n.m.r. studies of various stereostructural forms of poly(N-vinyl carbazole)

Three different stereostructural forms of poly(N-vinyl carbazole) (PVK) have been prepared using cationic (AlCl₃ and BF₃(CH₂CH₃)₂O) and radical (azobisisobutyronitrile) initiators. The dipole moment per repeat unit of PVK has been determined and correlated with ¹³C n.m.r. spectra of the methine and methylene carbon absorptions for fractions of PVK in solution in 1,4-dioxan. The dielectric data for cationically prepared PVK appear to indicate a random coil configuration or possibly a rod-like structure in which the dipole moment vectors of the carbazole groups are randomly oriented but remain approximately perpendicular to the long axis of the molecule. For each type of PVK examined the repeat unit dipole moment was observed to be independent of molecular weight over the range 10⁴–10⁷ and insensitive to polydispersity.     

Prospects for carbon-13 nuclear magnetic resonance analysis of solid fossil-fuel materials

Because of excessive line broadening in solids due to magnetic dipole—dipole interactions and chemical shift anisotropies, and because of long spin-lattice relaxation times, standard continuous wave (CW) or pulse Fourier transform techniques do not normally yield structurally informative ¹³C n.m.r. spectra from solid samples. However, the techniques of dipolar decoupling, cross polarization and magic-angle spinning show great promise for routine ¹³C n.m.r. studies of solids. Applications of these techniques to analysis of anthracite, lignite and algal coal samples, and to oil shale and kerogen samples, are discussed. It is shown that cross-polarization spectra obtained with dipolar decoupling display chemical shift anisotropy which interferes with attempts to distinguish the resonances of aromatic and aliphatic carbons. However, with magic-angle spinning the distinction can be made. Prospects and potential difficulties with applications of these techniques are discussed.     

Influence of temperature on the hydrogenation of Australian Loy-Yang brown coal. 2. Structural analysis of the asphaltene fractions

A study is made of the asphaltene fractions produced by hydroliquefaction of an Australian Loy-Yang brown coal at temperatures ranging from 300 to 500 °C. A combination of Fourier-Transform ¹³C n.m.r. conventional proton n.m.r., i.r. and u.v. spectroscopy is used in conjunction with previously published data to define representative average chemical structures. Results indicate that the asphaltenes increase in aromaticity as the hydrogenation temperature rises, with a rapid change occurring near 450 °C. Furthermore, the asphaltenes formed at the highest hydrogenation temperature of 500 °C appear to consist of dehydrogenated derivatives of species produced at lower temperatures. Most of the saturated carbon atoms in all fractions occur in condensed cyclic structures with very few side-chains or methylene bridges. Because of this, the commonly assumed value of 0.50 for the saturated carbon to hydrogen atomic ratio used in the Brown-Ladner equation may be in error if applied to systems of this type. Below 450 °C the aromatic component of the asphaltenes consists mainly of isolated naphthalenic and mononuclear structures. Below 400 °C a small but significant number of carbon atoms are present in alkyl chains at least 8 carbon atoms long.     

A spectroscopic investigation of the banding or lithotypes occurring in Victorian brown coal seams

Solid-state ¹³C n.m.r. and infrared spectroscopy were used to investigate the gross differences in chemical structural between the five primary lithotypes or coal bands present in Victorian brown coal seams. Examination of a series of coal lithotypes, along with their insoluble kerogen fractions, indicated significant structural variation between the light and dark samples, particularly in their aromaticities and levels of lignin-derived structures. Comparison of K₂₉₂₀ (cm mg⁻¹) and K₁₇₁₀ (cm mg⁻¹) infrared data revealed that the aliphatic C-H content did not exhibit the level of lithotype dependence shown by carbonyl/carboxyl concentration. Correlation with ¹³C n.m.r. data revealed a direct inverse relation between aromaticity and carbonyl/carboxyl content. Aromaticity and carbonyl/carboxyl content are suggested to be the main gross chemical structural properties affecting lithotype classification. Investigation of a depth profile of the light lithotype revealed that gross structural variation between the samples did not result from rank effects. Rather, the depth profile reflects minor depositional variations which did not affect their lithotype classification. The gross chemical characterization of the lithotypes supports paleobotanical interpretation regarding the different depositional environments and inputs responsible for the observed coal banding.     

Estimation of aliphatic H/C ratios for coal liquefaction products by spin-echo 13C n.m.r.

The direct estimation of aliphatic H/C ratios for coal liquefaction products using a part-coupled spinecho (PCSE) ¹³C n.m.r. method is described. The method, which enables proportions of aliphatic C, CH, CH₂ and CH₃ groups to be deduced, has been applied to a low molecular weight (<200) aromatic fraction of hydrogenated anthracene oil (HAO) and to higher molecular weight (?280) aromatic and asphaltene fractions of supercritical gas (SCG) extracts and a hydrogenation residue (pitch). Aliphatic H/C ratios for these occur in the range 1.9-2.3, the SCG extract fractions having the highest values because they contain significantly more CH₃ and less CH than the HAO and pitch fractions.     

C nuclear magnetic resonance spectral analysis of stereosequences in ethylene-propylene copolymer

A number of split peaks dependent on both comonomer sequences and stereosequences were observed in the ¹³C nuclear magnetic resonance (n.m.r.) spectrum of ethylene-propylene (E-P) copolymer. The ¹³C chemical shifts of methylene carbon in stereoisomers of the respective hexad comonomer sequences were predicted by a chemical-shift calculation using the gamma effect on ¹³C chemical shifts and Mark's rotational isomeric state model for E-P copolymer. Assignments of the split peaks that arise from different hexad stereosequences were given by comparison between the observed and calculated chemical shifts. Reference was made to the hexad assignments of comonomer-sequence-dependent peak splittings determined in our previous calculation of ¹³C n.m.r. chemical shifts of stereoregular E-P copolymers. The tacticities were estimated for successive (not separated by ethylene units) propylene units in the hexad sequences.     

宁夏庆华煤镜质组和惰质组显微组分的分子结构及对比分析

使用密度梯度离心法对宁夏庆华煤的显微组分进行分离,获得煤的镜质组和惰质组。通过元素分析、X射线光电子能谱（XPS）、固体¹³C核磁共振（¹³C NMR）技术、傅里叶变换红外光谱（FTIR）和X射线衍射（XRD）技术等表征手段对不同显微组分进行物性表征。进一步基于统计平均的分子结构近似结合分子模拟计算,确定庆华煤镜质组和惰质组显微组分的分子结构可分别表示为C₂₆₉H₁₉₆N₄O₁₃S和C₂₅₅H₁₇₉N₃O₁₄S。通过FTIR光谱与¹³C NMR光谱验证,从而实现了不同显微组分的分子结构描述。对两种显微组分的分子模型和结构参数进行了系统对比分析,发现镜质组的芳碳百分数为51.95,惰质组的芳碳百分数为62.16。镜质组模型中芳碳结构数目较少,脂肪碳结构丰富,不饱和度较小,还原度最大。惰质组模型中芳碳结构数量最大,脂肪碳结构数目少,不饱和度最大,煤化程度高。镜质组在原煤中含量高,是原煤的主要组成。惰质组的含量少且大分子结构缩合度高,分布在镜质组构成的基体中。     

C cross-polarization n.m.r. examination of the Glen Davis oil shale deposit

The use of solid-state ¹³C cross-polarization n.m.r. for rapid analysis of bore cores is demonstrated by examination of subsections of a Glen Davis oil shale bore. The determined aromaticities, f_a, differ widely between subsections indicating large variability in potential oil yields. The variation does not correlate with depth of subsection but is shown to correlate well with maceral composition. The correlation found previously by Zilm and co-workers (Fuel 1981, 60, 717) between f_a, determined by solid-state ¹³C n.m.r., and wt% fixed carbon for a range of macerals is found to be supported by the data for Glen Davis subsections which are mixtures of all three maceral types.     

Studies on copolymers of acrylonitrile with resins of furfuryl alcohol: 1. Preparation and thermal properties

Copolymers of acrylonitrile with a furfuryl alcohol resin have been prepared by a free radical reaction, and have been characterized by n.m.r. and i.r. spectroscopy. Their t.g.a. has been performed in air and in a nitrogen atmosphere, to permit the recognition of a number of stages in the weight loss process. D.s.c., also in air and in nitrogen, has identified a number of exothermic and one endothermic process in the copolymers. Solid state cross-polarization/magic angle spinning ¹³C n.m.r. spectroscopy and i.r. spectroscopy has been used to obtain some insight into the chemistry of the various chemical changes, which in air are completed by combustion and in nitrogen leave a carbon.     

Evaluation of a delayed coking process by H and C n.m.r. spectroscopy: 2. Detailed interpretation of liquid n.m.r. spectra

The ¹H and ¹³C nuclear magnetic resonance (n.m.r.) spectra of a delayed coking feedstock and products, presented in a previous paper, are analysed here in detail by matching results from inspection of both nuclei. The conventional spectra of whole samples are used in combination with elemental analysis data, and substantial agreement is obtained. Differences are explored to yield valuable information. Interpretation of some band assignments is modified to account for new results. This approach results in a detailed quantitative estimation of a few key structures that contain the main functional groups that characterize these petroleum fractions.     

霍林河褐煤化学结构特性的13C NMR与FTIR对比分析

采用¹³C NMR及FTIR对霍林河褐煤的化学结构特性进行深入分析,通过¹³C NMR计算得到霍林河褐煤包含34.32%的脂肪族碳、61.25%的芳香族碳以及4.43%的羰基碳。平均每个芳环团簇包含1~2个芳香环,每个芳香环中平均碳原子取代数为3~4。平均亚甲基碳链数为1.4,烷链支化度为25.47%,说明脂肪族多以短链分支形式存在。通过对霍林河褐煤红外光谱进行分峰拟合,计算得到煤的FTIR结构参数（平均亚甲基碳链数、芳香环取代度、烷链支化度）与¹³C NMR计算结果相吻合。虽然芳碳率（f_ar-F=55.37%）与¹³C NMR计算结果存在一定的偏差,但是FTIR很大程度上仍然可以反映煤的碳骨架结构特性。     

Studies on the evolution of asphaltene structure during hydroconversion of petroleum residues

The evolution of asphaltenes has been studied under hydroconversion conditions with an ebullated bed on a Buzurgan (Middle East) feedstock. A bench unit was used to produce effluents in residue conversion conditions ranging from 55 to 85 wt.%. In those conditions, asphaltene conversion ranged 62–89 wt.%. Asphaltenes from the feedstock and unconverted asphaltenes have been characterized using Size Exclusion Chromatography to evaluate asphaltene size, and ¹³C Nuclear Magnetic Resonance to evaluate the evolution of the average molecular structure parameters of asphaltenes. Results obtained were compared to results obtained at moderate residue conversion levels in a fixed bed.

The work clearly shows that unconverted asphaltene evolution is continuous. Unit size decreases with increasing conversion while the aromaticity of the asphaltenes increases due to dealkylation. Our results suggest that the remaining asphaltenes are dissociated in smaller aggregates around 50% conversion. Below this level, asphaltene evolution may be related to dissociation mechanisms. Above 50% conversion, the chemical structure of asphaltene units still significantly evolves through dealkylation mechanisms, leading to fairly condensed structures that remain at high conversion. Based on these results, an attempt was conducted to interpret the evolution of unconverted asphaltenes as a function of residue conversion level using a simple molecular reconstruction method.     

沙特原油活性组分的结构对油水界面性质的影响

测定了从沙特原油中分离出的胶质和沥青质的红外、紫外光谱和相对分子质量。对含有胶质、沥青质的模拟油和模拟水体系,测定了其界面张力和界面剪切黏度。胶质和沥青质的相对分子质量分别为497和1 786;光谱分析结果表明,沥青质比胶质含有更多的芳香环结构。含胶质和沥青质体系的界面张力分别是33.205 8 mN/m、31.732 5 mN/m,相差不大。对于界面剪切黏度,沥青质体系远大于胶质体系,同在100 mg/L,胶质体系剪切速率在0-0.5 rad/s时,界面剪切黏度最大不超过0.002 5 mN/m,而沥青质体系剪切速率在0.3 rad/s下,界面剪切黏度最大值大于1.000 0 mN/m,并且其曲线具有吸附曲线的特征,沥青质体系具有较强的界面膜,其界面膜的形成经历了从液态扩张膜到液态凝聚膜的变化过程。界面膜强度的大小与界面活性物质的相对分子质量的大小和芳香环结构含量的多少有关。     

Use of Fourier Transform infrared spectroscopy for determining oil shale properties

Fourier Transform infrared analysis has been examined as a technique for evaluating the oil-yielding potential of raw oil shales. The technique was developed recently for analysing coals, and gives a quantitative measure of aliphatic, aromatic and hydroxyl hydrogen. From these measurements, it was verified that an approximate rectilinear relation exists between the oil yield of an oil shale as determined by Fischer assay and the aliphatic hydrogen concentration in the shale. An equivalent relation was established previously between the oil yield and the aliphatic carbon concentration as determined by ¹³C cross polarization n.m.r. When the oil yield is expressed in weight per cent, it is seen that the yield is only slightly less than the weight per cent of aliphatic hydrocarbons. This suggests that, under the conditions of the Fischer assay, there is almost complete conversion of the aliphatic components to oil.