Zur Anwendung von Lanthanoid-Verschiebungsreagenzien bei der NMR-spektroskopischen Untersuchung von Gemischen monofunktioneller Kohlenwasserstoffe

Application of Lanthanide Shift Reagents in ¹H-N.M.R.-Spectroscopic Investigations of Mixtures of Monofunctional Hydrocarbons The influence of n.m.r. shift reagents on the ¹H-n.m.r.-spectra of mixtures has been investigated. Hydrocarbons of the type CH₃(CH₂)_nX (X =  OH,  CHO,  COR,  COOCH₃,  COOH,  OR with R = Methyl-, Ethyl-, n-Propyl-, n-Butyl- and n = 1,2) served as model substances. The components of the mixtures compete with the shift reagent. Relative equilibrium constants have been calculated to describe this behavior in mixtures. Several equations have been deduced and tested to describe the induced shifts of the protons in mixtures. These equations are applicable to qualitative and quantitative analysis of unknown mixtures.     

Oil-shale analysis by CP/MAS-13C n.m.r. spectroscopy

Solid-state ¹³C n.m.r. (CP/MAS-¹³C n.m.r.) spectroscopy provides a direct method for estimating potential oil yields of oil shale formations. Relative aliphatic resonance areas correlate linearly with oil yield and provide a method for oil yield estimation that obviates the need to determine weight per cent organic carbon for each specimen. This direct measurement is performed using an internal area standard, the carbonyl resonance of N-(2-¹³C-propanonyl)-N,N,N-trimethylammonium chloride, to monitor spectrometer sensitivity. Oil shale samples obtained as a function of depth at a site in the Mahogany Zone of the Green River Formation show a near-constant aliphatic carbon fraction, f_al ≡ (1?f_a), and a twofold, nonlinear variation in oil yield over the vertical dimension of the sampling. Aliphatic carbon resonance band shape changes among these samples are interpreted qualitatively as reflecting a two component mixture composed of the condensed alicyclic structures which link together to form the kerogen matrix and an n.m.r.-distinct but not necessarily chemically distinct contribution from normal-long chain hydrocarbon residues.     

Liquefaction reaction of coal: 2. Structural correlation between coal and its liquefaction products

The structural correlation between coal and its liquefaction products has been examined using cross-polarization, magic angle spinning (CP/MAS) ¹³C n.m.r. and field ionization mass spectrometry (f.i.m.s.). The CH₂/aromatic carbon ratios of all solid products (asphaltene, preasphaltene and residue) were close to the corrected +CH₂/aromatic carbon ratio for the coal. This suggests that the ring structure of the structural unit of each solid product is essentially similar to that of the parent coal, except for a difference in the degree of polymerization of the structural units. The CH₂/aromatic carbon ratios of aromatic ring-type oil fractions also correlated with the corrected ratio for the coal, although they were larger. The z series distribution obtained from the f.i.m.s. of oil fractions revealed that coal with a higher CH₂/aromatic carbon ratio produced an oil rich in naphthenic structures.     

Nature of hydrogen bonding in coal-derived asphaltenes

Near-infrared (n.i.r.) and proton magnetic resonance (p.m.r.) studies are reported of hydrogen bonding between the hydroxyl group of o-phenylphenol (OPP) and two coal-derived asphaltenes, and their acid and base components. The asphaltenes were isolated from two centrifuged liquid product (CLP) samples prepared from West Virginia, Ireland Mine bituminous coal under the same reaction conditions, except that CLP FB44–56 was prepared with the reactor charged with a CoMo catalyst, while CLP FB50-17 was prepared with glass pellets in place of the catalyst. The base asphaltene components from both FB44–56 and FB50-17 cause a decrease in the OPPOH absorbance at 1.44 μm in CS₂ and a downfield shift of the OPPOH p.m.r. resonance in CS₂, while these changes are not observed for the original asphaltenes or their acid components. Furthermore, the base asphaltene component from CLP 44–56 is more effective in decreasing the OPPOH absorbance when compared with the base asphaltene component from CLP FB50-17. Also, the absorbance of a pentane-soluble fraction of the acid asphaltene component at 1.42 μm in CS₂ from CLP FB50-17 is decreased upon addition of the corresponding base asphaltene component. Our results lead to the conclusion that the use of a CoMo catalyst leads to a base asphaltene component of lower molecular weight and higher hydrogen-bond acceptor strength.     

Determination of aromatic hydrocarbon fraction in oil shale by 13C n.m.r. with magic-angle spinning

A method for estimation of aromatic content in oil shales is demonstrated. Magic-angle spinning at 2 kHz is shown to remove chemical shift anisotropy to a sufficient degree to resolve aromatic and aliphatic ¹³C n.m.r. spectral regions for a lithic oil shale specimen. The proton and carbon n.m.r. relaxation parameters are such as to allow room-temperature use of this proton-enhanced ¹³C n.m.r. technique as a quantitative analytical tool. Cross polarization times of a millisecond or less and experiment repetition periods of 0.5 s or less are optimum. The specimen examined is represented by an aromatic carbon fraction 0.264 ± 0.007; this determination is quite insensitive to the proton-carbon cross polarization time. Spectra for kerogen, shale oil, and dawsonite are also presented. Dawsonite may interfere in the determination of the aromatic fraction.     

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.     

N.m.r. study of US Eastern and Western shale oils produced by pyrolysis and hydropyrolysis

Shale oils produced from US Eastern and Western oil shales by pyrolysis and hydropyrolysis processes have been investigated by both ¹H and ¹³C high-resolution n.m.r. techniques. Eastern shale oils produced by hydropyrolysis, and subsequently hydrotreated, were also included. From the n.m.r. data of the shale oils, the average molecular structure parameters were calculated. These parameters quantitatively represent the differences observed in the n.m.r. spectra of the various shale oils because of changes in the chemical composition. Mol percentages of aromatics, olefins, and alkanes were also determined for the shale oils, and show that the composition of the shale oil is dependent upon the geographic origin of the oil shale, the pyrolysis method, and the hydrogenation process. In addition to the study of shale oils, solid-state ¹³C n.m.r. spectra of Eastern and Western oil shales before and after pyrolysis and hydropyrolysis were obtained. The spectral data show that the carbon aromaticities for the Eastern oil shales and shale oils are higher than for the Western oil shale and shale oils. The data also show that hydropyrolysis relative to pyrolysis reduces the amount of residual organic carbon remaining on the spent shales. Carbon aromaticity data for both oil shale and shale oil suggest that the organic moieties present in kerogen may be retained in the shale oils to a greater extent after hydropyrolysis than after pyrolysis.     

Hydrocarbon structural group analysis of Athabasca asphaltene and its g.p.c. fractions by C n.m.r.

Asphaltene from the Athabasca oil sand bitumen separated according to molecular weight by gel permeation chromatography was examined by high resolution solution-state ¹³C and ¹H and solid state ¹³C n.m.r. Integration of the inverse gated decoupled solution state and CP/MAS ¹³C n.m.r. spectra gave the aromaticity of each fraction as well as the relative number of carbon atoms responsible for well resolved signals in the aliphatic portion of the spectra. A two-pulse spin-echo ¹³C n.m.r. sequence in the solution state, and dipolar dephasing in the solid state, permitted the assignment of each aliphatic carbon signal to a methyl, methylene, or methine carbon; no quaternary aliphatic carbons were observed. These signals show that the aromatic core of the asphaltene is surrounded by alkyl chains with a mean length of 7.7 for the lowest molecular weight fraction (MW 1200), increasing to 12 for the highest MW fraction (MW 16900). Aromaticity of the fractions obtained from solution spectra ranged from 34 to 48%, the highest aromaticity being associated with the lowest molecular weight asphaltenes. In the solid state, the aromaticity ranged from 31 to 42 %. The degree of branching ranged from 0.5 per chain for the low MW asphaltene to 1.0 for the high MW fraction. The highest naphthenic carbon content was found in the high MW fractions; the 1200 MW fraction appeared to be nearly devoid of such carbon, this fraction having a much higher aromaticity than the second-lowest MW fraction.     

Zur Beschreibung der Wechselwirkung zwischen p-substituierten Benzaldehyden und NMR-Verschiebungsreagenzien

Investigations to the Interaction between p-Substituted Benzaldehydes and N.M.R.-Shift Reagences The influence of n.m.r. shift reagents (Eu(fod)₃ and Pr(fod)₃) on the chemical shifts of p-dimethylaminobenzaldehyde has been investigated at ¹³C and ¹H-n.m.r. spectroscopy. The induced shifts of the protons are quantitatively explained on the basis of pseudocontact interaction. In ¹³C-n.m.r. spectra significant contact interactions have also been noted. The ¹³C induced shifts have been separated into pseudocontact and contact contributions by two different methods. Calculations of relative equilibrium constants in mixtures have been carried out for p-dimethylaminobenzaldehyde, p-nitrobenzaldehyde, anisaldehyde and benzaldehyde. The relative equilibrium constants show a good correlation with the Hammett substituent constants.     

1H n.m.r. technique for characterization of polymerized petroleum pitches

A new proton n.m.r. technique has been developed for the chemical characterization of polymerized petroleum pitches with pyridine-insoluble contents as high as 80%. The polymerized pitches were completely solubilized for conventional ¹H n.m.r. evaluation in a mixed solvent system consisting of S₂Cl₂-SO₂Cl₂. Although solubilization occurs via the addition of chlorine to the polynuclear aromatic rings, the n.m.r. spectra can still be quantitatively interpreted. Several applications are discussed.     

Pulsed n.m.r. of cis-polyisoprene: 2

Pulsed n.m.r. spin-spin relaxation time measurements are reported for a commercial whole polymer sample of cis-polyisoprene which has been crosslinked to varying extents by γ-irradiation. The spin-spin relaxation decays at 150°C consist of two components, T_2S and T_2L, which are attributed to protons in a network structure (entangled or crosslinked) and in non-network molecules respectively. Comparison of the n.m.r. data with solubility measurements, which only detect the presence of a crosslinked network, provides a value for the average molecular weight for entanglements which is in the region of 40 000 to 50 000.     

Aromatic products of 340 °C supercritical-toluene extraction of two Turkish lignites: an n.m.r. study

Fractions of Elbistan and Seyitomer (Turkish) lignites, extracted with supercritical toluene at 340 °C and 8 MPa, have been separated by solvent extraction and silica-gel chromatography. Analyses by n.m.r. and i.r. spectroscopies and other methods have been combined in structural-analysis schemes to yield information about the average molecule in aromatic extracts. Carbon aromaticities, f_a, derived from 22.63 MHz ¹H-decoupled pulse Fourier-transform (PFT) ¹³C-n.m.r. are more widely spread for Elbistan (0.34–0.56) than for Seyitomer (0.40–0.43), and are lower than for supercritical-gas (SCG) products from bituminous coals. ¹³C-n.m.r. also reveals the presence of aromatic ether-O in polar fractions. Narrow aromatic signals in 100 MHz ¹H-n.m.r. spectra suggest the presence of single-aromatic-ring average structures. In the hexane-soluble aromatics, 27% (Elbistan) and 29% (Seyitomer) of the available sites are substituted by alkyI groups, some of which are at least eight carbon atoms long; the hexane-soluble polar and asphaltene/asphaltol fractions contain fewer such groups.     

E.s.r. of Alberta tar sand bitumen and thermally hydrocracked products

A study of the vanadium and free radical species present in Athabasca bitumen and thermally upgraded products from a hydrocracking pilot plant was carried out. The samples were separated into asphaltene, chloroform resin, tetrahydrofuran resin and oil components, and the fractions studied by electron spin resonance. All samples except the oil fraction contained vanadyl (VO²⁺) ions and free radicals. It was found that even mild thermal treatment of bitumen produced considerable redistribution of vanadyl groups among the fractions, whereas at the severest hydrocracking conditions 94 wt% of all vanadyl groups were associated with the asphaltene fractions compared with only 58.5 wt% in the original bitumen. As the hydrocracking severity increased, the asphaltene vanadyl concentration initially increased above the value for unreacted bitumen and then decreased to a lower value. On the other hand, the resin vanadyl concentration decreased continuously and more rapidly than asphaltene vanadyl concentration. This indicates that vanadyl groups associated with the resin fractions are less stable than those associated with the asphaltenes and also suggests that transfer of vanadyl groups from the resin fractions to asphaltene predominates at low severity while removal of vanadyl groups predominates at high severity. The average spin Hamiltonian parameters showed that the chemical environment of vanadyl ions in the THF resins was significantly different from the vanadyl environment in the other two fractions.     

Monomer sequence determinations of aryl ether sulphone copolymers as determined by 13C n.m.r.

The monomer sequence distributions of three types of aryl ether sulphone copolymers have been determined by ¹³C n.m.r. spectroscopy. Two amorphous aryl ether sulphone copolymers were shown to have transetherified (or ether interchanged) during polymerisation to become random copolymers. The residues in these copolymers were (i)—OøOøSO₂øS—and (ii)—OøSO₂øøSO₂ø—-where ø denotes 1,4-phenylene. Copolymers of 50:50 aryl ether sulphone and aryl ether ketone made from different combinations of monomers were found to have different solubilities in dimethyl sulphoxide, and from ¹³C n.m.r. data this was shown to correlate with the amount of transetherification which had taken place during the polymerisations. The ¹³C n.m.r. chemical shifts for some of the carbon nuclei in these polymers were sensititive to functional groups situated even as far away as three or four aromatic nuclei along the polymer chain.     

Quantitative aspects of solid state 13C n.m.r. of coals and related materials

The quantitative aspects of cross-polarization (CP), which is used in conjunction with dipolar decoupling and magic-angle rotation to obtain high resolution ¹³C n.m.r. spectra of coals, have been studied using a bituminous coal (82 wt% C, dmmf basis) and asphaltenes from an extract of the same coal. The condition for obtaining reliable quantitative data, that rotating frame ¹H relaxation times (T_1p′ these govern the extent of CP) are much longer than the time required to polarize the carbons present (≈1 ms), was met for the asphaltenes. In contrast, about half the protons in the coal have T_1p5 of ≈ ? 1 ms, these times being too short to allow CP of all the carbons. Although the aromaticities obtained for this coal were fairly constant (≈0.75) using (CP) contact times > 0.5 ms, the total peak intensity decreased markedly as the contact time was increased and was much less than that for the asphaltenes. These results indicate that not all the carbons in bituminous coals are observed by CP and, as a consequence, aromaticities reported in the literature for some bituminous coals appear to be low.     

Comparison of the chemical structure of coal hydrogenation products,athabasca tar sand bitumen and Green River shale oil

Coal hydrogenation products, Athabasca tar sand bitumen, and Green River shale oil produced by retorting were analyzed by the Brown—Ladner method and the Takeya et al. method on the basis of elemental analysis and ¹H-NMR data, by ¹³C-NMR spectroscopy and by FT-IR spectroscopy. Structural characteristics were compared.The results show that the chemical structure of oils from Green River shale oil and Athabasca tar sand bitumen, and the oils produced in the initial stage of hydrogenation of Taiheiyo coal and Clear Creek, Utah, coal is characterized as monomers consisting of units of one aromatic ring substituted highly with C_3–6 aliphatic chains and heteroatom-containing functional groups. The chemical structure of asphaltenes from Green River shale oil and Athabasca tar sand bitumen is characterized by oligomers consisting of units of 1–2 aromatic rings substituted highly with C_3–5 aliphatic chains and heteroatom-containing functional groups. The chemical structure of asphaltenes from coal hydrogenation is characterized by dimers and/or trimers of unit structures of 2 to 5 condensed aromatic rings, substituted moderately with C_2–5 aliphatic chains and heteroatom-containing functional groups.The close agreement between fa(¹H-NMR) and fa(¹³C-NMR) for Green River shale oil derivatives and Athabasca tar sand derivatives indicates that the assumption of 2 for the atomic H/C ratio of aliphatic structures is reasonable. For coal hydrogenation products, a value of 1.6–1.7 for the H/C ratio of aliphatic structures would be more reasonable.     

Extraction of bitumen with sub- and supercritical water

The sub- and supercritical water extractions of Athabasca oil sand bitumens were studied using a micro reactor. The experiments were carried out in the temperature range of 360–380 °C, pressure 15–30 MPa and water density 0.07–0.65 g/cm³ for 0–2 hrs. The extraction conversion of bitumens increased with solvent power and temperature. A maximum conversion of 24% was obtained after 90 min extraction at the supercritical condition. Hydrogen and carbon mono-oxide were not detected in sub-critical region but in the supercritical region. The supercritical condition was favorable to the hydrogen formation for bitumen extraction. The extraction products were upgraded relative to the original bitumens due to direct hydrolysis of low-energy linkage and H₂ formed by water gas shift reaction in supercritical condition. 18% of initial sulfur in bitumen can be removed at maximum conversion condition. The asphaltene contents of the residue were significantly higher than that of original bitumen due to preferential extraction of aromatic compounds in supercritical condition.