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.     

Effect of temperature on tacticity in thermal polymerization of p-methylstyrene by 13C NMR spectroscopy

Poly(p-methylstyrene) (Pp-MS) was synthesized at three different temperatures of 50, 150 and 250?°C via bulk thermal polymerization method. The assignment of all stereosequences at triad and pentad levels for two quaternary aromatic carbons and hexad level for methylene carbon was carried out by ¹³C liquid nuclear magnetic resonance spectroscopy (NMR) in deuterated chloroform at similar conditions. The probability of meso addition (P _m) was calculated from second quaternary aromatic carbon and used to predict the relative intensities of methylene and first quaternary aromatic carbon by Bernoullian and first-order Markov statistical models. The results were compared with experimental data. It is shown that the Bernoullian statistics fit better than first-order Markov model for all three samples. The results indicate that P _m increases by increasing polymerization temperature. The corresponding P _m values determined for synthesized Pp-MSs at 50, 150 and 250?°C were 0.383, 0.392 and 0.404, respectively. It was observed that higher resolutions and better splitting patterns were achievable by increasing the NMR acquisition temperature from 20 to 50?°C. When temperature increased during NMR acquisition, the resolution improved for the first and second quaternary aromatic carbons and methylene carbon, though there was no splitting pattern observed for methyl carbon atom at the para-position of the aromatic ring.     

Relaxation of 13C and 15N nuclei by solvent-refined coal

The effects of changing various spectroscopic parameters on the solid-state and solution ¹³C-nuclear magnetic resonance (n.m.r.) spectra of solvent-refined coal have been investigated. Solution spectra were obtained with the use of broad band decoupling, inverse gated decoupling and coupling techniques. Conventional relaxation reagent (Cr(acac)₃) was sometimes added to the solvent-refined coal. The effects of pulse delay on the total signal intensity, and on the intensity of the signal from aromatic carbon have been measured. The results show that inverse gated decoupling with pulse delays of 10 s is needed for complete relaxation of solvent-refined coal, but pulse delays of 6 s can give accurate estimations of aromaticity. However, it is recommended that conventional relaxation reagent such as Cr(acac)₃ be added to ensure relaxation if shorter pulse delays are used. The effect of solvent-refined coal on relaxation of some pure compounds in solution has also been studied. Solvent-refined coal acts as a relaxation reagent on ¹³C nuclei in benzene, toluene and ethylbenzene. It can also relax ¹⁵N nuclei in aniline, N,N-dimethylaniline and nitromethane. Spin-lattice relaxation times (T₁'s) of selected nuclei have been measured and the contribution of solvent-refined coal to relaxation (T₁SRC) has been calculated. Solid-state 13C-n.m.r. spectra have been obtained using the cross-polarization (CP) technique with magic-angle sample spinning (MASS). A variety of cross-polarization times and recycle times have been used. The results show that no serious errors in measurement of aromaticity (f_a) are caused by using a contact time as short as 1 ms and a recycle time of 0.3 s. There is good agreement between f_a's obtained by solution and solid-state n.m.r., and as solid-state spectra can be obtained in only a fraction of the time needed to obtain a solution spectrum (≈$\text{1}\text{20th}$), CP-n.m.r. is the method of choice for analysis of f_a of solvent-refined coal. The results also show that CP-MASS n.m.r. can be used to estimate the fraction of aromatic carbon which is unprotonated in solvent-refined coal and, hence, indirectly, the fraction of hydrogen which is aromatic.     

Quantitative FT 13C n.m.r. of solvent-refined coals using sym-triazine as solvent

Aromaticities (f_a) determined for several solvent-refined coals (SRC) by ¹³C n.m.r. in sym-triazine solution and by the Brown and Ladner ¹H n.m.r. technique have been found to be the same within experimental error (0.01). Use of sym-triazine to determine the f_a of the soluble and insoluble fractions of a SRC in several solvents showed that the soluble fraction reflected reasonably accurately the properties of the whole sample for dioxan, carbon disulphide, chloroform and benzene extracts. The properties of the insoluble fraction varied only slightly. A more detailed analysis of the aromatic region of the ¹³C n.m.r. spectrum has led to some useful structural relations.     

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.     

Synthesis and properties of star-like wholly aromatic polyester fibers

Novel star-like wholly aromatic copolyesters having four arms based on a tetraamine star core, p- and m- hydroxybenzoic acids and 6-hydroxy-2-naphthoic acid have been successfully synthesized and spun into fibers for the investigation of the effect of the star-like structure on improving compressive properties of the fiber. The reactivity of the star core was demonstrated using a model compound with FTIR, ¹H and ¹³C NMR spectroscopy. The ¹³C NMR spectrum of the star-like terpolymer having a molar ratio of 10:1 of the monomers to star core showed a characteristic peak at around δ62 ppm which corresponds to a tetra-substituted carbon and thereby demonstrates that the star core was really incorporated into the polymer. The star-like copolyester exhibited a clear stir opalescence and liquid crystalline morphology in the temperature range of 150-280 °C. However, no transition was observed in the DSC thermogram except a clear T_g at 110 °C. The star-like terpolymer fiber, prepared from a polymer with a molar ratio of 500:1 for the monomers to imide core, was spun in the liquid crystalline state at 180 °C. Fiber structure and properties have been studied.     

13C1H Cross-polarization nuclear magnetic resonance spectra of macerals from coal

The carbon aromaticities (f_a) of vitrinite, exinite, micrinite and fusinite from a high-volatile A bituminous coal have been determined by ¹³C¹H cross-polarization nuclear magnetic resonance spectrometry. Values of f_a for the four macerals were found to decrease in the order: fusinite > micrinite ≈ vitrinite > exinite. Estimates of the average ring size using the f_a value and the elemental composition of each macerai indicated that the fusinite contained the largest polynuclear condensed aromatic ring system (> 5 rings) whereas the mean structural unit of the vitrinite contains 3–4 condensed rings.     

Characterization of whole coals by 13C CP/MAS spectroscopy at high field

Solid-state 50-MHz ¹³C spectra essentially free of spinning sidebands have been constructed for three bituminous coals by the addition of echo spectra having phase-altered spinning sidebands (PASS). The echo spectra are produced by a modified version of the Dixon pulse sequence. Quantitative analysis of the aromatic carbon content (f_a) from PASS spectra for the three coals compares favourably with results obtained by other methods. Values of f_a are found in the range 0.69–0.73. Removal of the unwanted spinning bands allows absorptions for specific structural units present in the coals to be distinguished and assigned. Spectra show an upfield shoulder at 13–15 ppm, and moderately intense absorptions at 20–24 ppm and ≈30 ppm which are characteristic of several aliphatic structures in different steric environments. In addition to the main aromatic band at ≈120 ppm, absorptions for substituted aromatic carbons appear at ≈140 and ≈155 ppm. Less intense signals from several carbonyl functional groups (160–190 ppm) and oxygen- and nitrogen-substituted aliphatic groups (50–90 ppm) are also present.     

A 13C n.m.r. study of the sulphonation of novolacs

A parameter scheme has been devised for predicting the ¹³C shifts of atoms in the aromatic rings of phenols substituted with SO^?₃, CH₂Ar and CH₃ in an alkaline medium, from the measured shifts of 30 different substituted benzene rings. The application of the scheme to novolacs is considered before the scheme is used to interpret the changes of chemical shift that occur upon sulphonation of one such sample. In the aromatic carbon region the sites of substitution on the rings are identified. In the upfield region of the spectrum a substantial alteration to the pattern of shifts from the bridging methylene groups was noted: once a ring had been sulphonated the methylene bridge might break to yield methylol groups, which then to a large extent reformed as methylene and dimethylene ether (CH₂OCH₂) links, but with an increased proportion of abutments on sites para with respect to the phenolic group.     

Formation and chemical structure of preasphaltenes in short residence time coal hydrogenolysis

The formation and chemical structure of preasphaltenes in short residence time coal hydrogenolysis were investigated. In short residence time coal hydrogenolysis, preasphaltenes are the major product. The maximum yield for this parametric study was obtained under reaction conditions of 500 °C and 21 s. The formation of preasphaltenes reached the maximum value in the initial stage of the liquefaction reaction. As the liquefaction reaction continued, the deoxygenation of preasphaltenes proceeded. However, the decrease in aromatic atoms bound to the hydroxy, methoxy and oxygen atoms of the diphenyl ether group (Arz.sbnd;O) is small, and the ArO functionality still remains abundant in preasphaltenes. Preasphaltene-I is characterized by carbon aromaticity (f_a) of 0.6–0.7, aromatic rings of from 1 to 3–5 per condensed aromatic ring system, 55–70% substitution of aromatic ring carbons and C_2–3 aliphatic substituents. The molecular weight ranges from 500 to 650, and is not much different from that of the asphaltenes. The f_a values based on the Brown-Ladner method and on solid state CP/MAS ¹³C n.m.r. spectra data agree closely.     

The characterization of coal tar pitches used in electrode binder manufacture by n.m.r. spectroscopy

Coal tar pitches dissolved in a mixed solvent system comprising S₂Cl₂ and SO₂Cl₂ were analysed by ¹H and ¹³C n.m.r. spectroscopy. The extensive chlorination of the pitch by this solvent unfortunately leads to serious underestimations in aromatic hydrogen concentrations when these solutions are examined by ¹H n.m.r. spectroscopy. However, quantitative data can be obtained using ¹³C n.m.r. spectroscopy where the carbon skeleton is unaffected by the extent of chlorination of the pitch. The ¹H n.m.r. spectra of individual aromatic compounds, similar to those found in coal tars have been recorded. The ¹H n.m.r. spectra confirmed that extensive chlorination of the aromatic nuclei had occurred which results in the non-quantitative estimation of hydrogen concentrations.     

Electrochemistry of polycyclic aromatic hydrocarbons in molten tetrabutylammonium nitrate

The oxidation and reduction of a series of polycyclic aromatic hydrocarbons have been studied in molten tetrabutylammonium nitrate at 150°C. On the oxidation side nitrated products are formed and on the reduction side butyl-substituted products were obtained. In this solvent, which is slightly unstable at 150°C, limiting cathodic process is the reduction of the NBu₄ ⁺ ion to tributylamine and butenes and the limiting anodic process is the oxidation of NBu₄ ⁺ to carbon dioxide. Attempts to trap the reactive intermediates produced electrochemically with added substances were unsuccessful.     

Investigation of aromatic carbon sites in materials derived from petroleum and coal using 13C n.m.r. methods

Aromatic C and CH carbon sites in a variety of petroleum and coal derived materials have been investigated using a ¹³C n.m.r. technique termed spin echo broad band off-resonance decoupling (SEBBORD). Only resonances due to non-protonated aromatic carbon sites are observed in SEBBORD spectra such that comparison with conventional ¹³C n.m.r. spectra enables differentiation between aromatic C and CH group resonances. Relative abundances of non-protonated aromatic carbon sites calculated from SEBBORD data are in good agreement with values derived from a combination of conventional¹H n.m.r., ¹³C n.m.r. and elemental analysis data. The occurrence of significant proportions of aromatic C intensity to high field of 129–130 ppm and of aromatic CH intensity to low field of 129–130 ppm has been found to be quite common. Consequently attempts to determine aromatic C and CH group abundances by partitioning conventional ¹³C n.m.r. spectra in the vicinity of 129–130 ppm can lead to considerable quantitative errors. SEBBORD provides more detailed information about aromatic carbon sites than can be obtained from conventional ¹³C n.m.r. spectra.     

Initial coke deposition on hydrotreating catalysts. Part II. Structure elucidation of initial coke on hydrodematallation catalysts

Kuwait atmospheric residue (KAR) was hydrodemetallized (HDM) over a commercial Mo/Al₂O₃ catalyst using a fixed-bed reactor unit. Initial coke deposition on the catalyst vs. time-on-stream (TOS) was studied by solid-state ¹³C NMR to derive structural information on the initial coke deposited in the first 240 h of TOS. ¹³C NMR spectral editing (cross-polarization technique in combination with the polarization inversion pulse sequence) was applied to distinguish on the one hand between quaternary and tertiary aromatic carbon and on the other hand between secondary and primary aliphatic carbon. Structural parameters, derived from those NMR measurements in combination with the aromaticity from single pulse excitation ¹³C NMR and the H/C ratio from elemental analysis, have been used to assemble the hypothetical structure of initial coke.The 1 h coke has nearly the same H/C ratio as the KAR and represents an intermediate between heavy coke generating molecules from KAR and real coke. In the following 12 h, aromatic carbon is accumulated and aromatic rings are dealkylated but the coke is still rich in hydrogen. As the carbon deposition slows down (after 50 h) further aromatic carbon is built-up and aliphatic carbon decreases. After 120 h the hydrogenation activity of the HDM catalyst is still high and prevents the coke from getting hydrogen depleted, merely the degree of alkyl-substitution has dropped compared with the start of run. With further increase of run time, carbon deposition reaches a steady state (240 h). As the analysis of a spent HDM catalyst (6500 h) from an industrial ARDS unit shows, throughout the following months of operation the porous hydrogen rich coke is increasingly converted into highly condensed polynuclear aromatic coke. THF-extraction of the used catalysts (TOS; 1, 12, 120, and 6500 h) has mainly removed small aromatic compounds with a high degree of alkyl-substitution.     

Application of new 13C n.m.r. techniques to the study of products from catalytic hydrodeoxygenation of SRC-II liquids

A middle-heavy SRC-II distillate (b.p. 230–455 °C), containing 3.0 wt% of oxygen, has been studied by means of ¹³C n.m.r. at 75, 100 and 125 MHz. The magnetization refocussing techniques INEPT and J-resolved two-dimensional Fourier transform have been utilized to demonstrate methods by which resonance line multiplicities may be determined in complex liquid mixtures. Products derived from the above coal liquid by hydrodeoxygenation at temperatures from 200 to 370 °C, using sulphided Co—Mo and Ni-W catalysts, were also examined. The fraction of aromatic carbon in the hydrotreated liquids was found to correlate directly with their C/H atomic ratio and inversely with the hydrogen content. Comparison of O/C atomic ratios with f_a values for these liquids indicates that hydrogen uptake < 260 °C is associated primarily with hydrogenolytic oxygen removal without attendant ring hydrogenation, while at temperatures between 260 and 350 °C hydrodeoxygenation is accompanied by ring hydrogenation and dealkylation reactions.     

Distribution of aliphatic and aromatic carbons in H-Coal liquids by quantitative 13C FT-n.m.r. spectroscopy

Three H-Coal liquids, ASO, ASB, and VSO, have been characterized by quantitative FT-n.m.r. spectroscopy. FT-parameters were chosen to allow determination of aromatic:aliphatic carbon ratios to within 1% and 2% error of the theoretical and the absolute number of aromatic and aliphatic carbons in a simulated coal liquid, respectively. The aromaticity, f_a, the C_ar:C_al ratio and, the absolute number of both the aromatic and the aliphatic carbons on a per mol basis, have been derived for each H-Coal liquid using c.m.r. in combination with other physical data. By analysis of the chemical shifts of the c.m.r. spectra, the carbon distributions in the H-Coal liquids have been estimated and compared in terms of six structural types. The molecular parameters thus derived are reasonable correlated with the average molecular structures proposed as working hypothesis for the molecular characterization of the three H-Coal liquids.     

The characterization of asphaltenes and preasphaltenes obtained under various coal liquefaction conditions

A CP-MAS ¹³C NMR study of asphaltenes and preasphaltenes obtained under various coal liquefaction conditions is reported. The carbon aromaticity, f_a, of the solid extracts from the reaction products has a close relation with the reaction conditions. By plotting f_a against the atomatic $\text{H}\text{C}$ ratio for these solid products on the characterization chart for model polycyclic aromatic compounds, the molecular structures with relation to the liquefaction pathway from coal to oil can be proposed.     

Xe NMR studies on carbon replicas of Y zeolite

¹²⁹Xe NMR spectroscopy of xenon gas adsorbed on carbon replicas of Y zeolite was carried out at room temperature. Corresponding carbon replicas have been prepared by using ethylene and HY zeolite in a pressure reactor. Xenon gas was adsorbed on the resulting carbon samples in the pressure range from 40 to 150 kPa. The plot of the chemical shift against xenon pressure was found to be a linear function in the investigated pressure range from 40 to 150 kPa. Intense and narrow peaks have been observed for the synthesized carbon samples indicating chemically pure samples. By comparison of the estimated chemical shift parameter δ_N→0 and the slope δ₁ of the shift versus density plots the existence of different pore sizes could be revealed. These observed differences can be attributed to different types of micropores generated by shrinkage effects during carbon liberation from the parent zeolite host. The obtained carbon replicas of Y zeolite were further characterized by elemental analysis, XPS, ¹³C MAS NMR and ESR spectroscopy.     

Quantitative appraisal of the interfacial anchoring state of polyaromatic hydrocarbons during the formation of C/C composites

The preferred anchoring state for polycyclic aromatic hydrocarbons (PAHs) pyrolyzed onto carbon substrates has been studied by semi-quantitative methods, examining their interfacial lattice arrangements. The samples were prepared by decomposing petroleum pitch inside carbon nanotubes resulting in a variety of crystallinities forming one-dimensional C/C composites. Studies indicate that the preferred anchoring state of PAH molecules depends on the nature of the substrate. Accordingly the PAHs in mesophase pitch should exhibit a face-on orientation on the carbonaceous substrates, including a graphite sheet, glassy carbon, and pyrolytic carbon. However, it showed that the anchoring state (face-on or edge-on) of PAH units can be altered even on carbonaceous substrates. The results demonstrated that in C/C composites the anchoring state is predominantly determined by the relative degree of crystallinity of the pitch/carbon substrate, and can be semi-quantitatively estimated using the I_D/I_G ratio from Raman spectra. Face-on anchoring is preferred when the I_D/I_G ratio of substrate is smaller (higher crystallinity) than that of the pyrolyzed precursor, whereas edge-on anchoring is favored when it is larger. Such an estimation method is useful in tailoring microstructures in the fabrication of C/C composites using PAH precursors.     

Preliminary studies on the aromaticity of Australian coals: Solid state n.m.r. techniques

The aromaticities of samples from nine Australian coal seams, including pairs of hand-picked vitrains and durains, have been determined by ¹³C cross-polarization n.m.r. spectroscopy with magic angle sample spinning. The results clearly show that the aromaticity (f_a) of the coals increases with increase in vitrinite reflectance and carbon content and decrease in atomic H/C ratio. For a given coal seam, durain (inertinite-rich coal) has a higher f_a value than vitrain (vitrinite-tich coal). The trends for carbon content and atomic H/C are in good agreement with results from North American coals, although the aromaticities of Australian coals obtained in this study appear to be slightly lower than some of those reported for North American coals of similar carbon content.