Alkane Chain Research Articles

Catalytic pyrolysis of lignite with clay catalyst activated with spent pickling liquor

AbstractSpent pickling liquor (SPL) is an acidic waste with rich iron content from the stainless steel production industry. Reusability of SPL as a catalytic activity promoter in bentonite clay is crucial for the catalytic pyrolysis of various materials like biomass, coal, and waste plastics. For this aim, the bentonite catalyst activated with the SPL nomenclatured as SPL‐treated bentonite (SPLAB) catalyst was employed in the catalytic pyrolysis of lignite for an oil product with high yield and quality. The SPL‐treated bentonite catalytic pyrolysis oil (SPLABO) for the conditions of the final temperature of 600°C, heating rate of 10°C/min, and catalyst ratio of 15 wt% had a yield of 26.35 ± 1.14 wt% and good fuel properties in view of the higher heating value of 35.23 MJ/kg and density of 1076.4 kg/m3 at 20°C. Moreover, it has a rich chemical content by means of monocyclic aromatics and shorter chain alkanes compared with that of the thermal activated bentonite oil (TABO). Based on the chemical structure analysis results of the SPLABO and TABO comparatively, it was concluded that the SPL agent used as a catalytic activity promoter led to a significant increase in the catalytic activity of bentonite catalyst.

Norbornene Monomer Effects and Mechanistic Insights in Binuclear Nickel-Catalyzed Olefin Chain Walking Copolymerizations

Norbornene Monomer Effects and Mechanistic Insights in Binuclear Nickel-Catalyzed Olefin Chain Walking Copolymerizations

NMR Studies on the Structure and Functions of Small Biomolecules with Highly Flexible Conformation

Abstract In this review, we deal with the flexible structures of small biomolecules and discuss how spontaneous conformational changes are related to their biological functions, mainly focusing on our recent research results. In particular, we applied nuclear magnetic resonance (NMR)-based methods to biomolecules that largely comprise methylene-dominant chain(s) by observing spin-spin coupling constants in solution NMR and quadrupolar interactions and chemical shift anisotropy in solid-state NMR. In the study of spermidine and spermine, we investigated how the shape of a molecule changes when the ammonium groups interact with polyanions such as ATP. In membrane lipid studies, we examined the orientation and conformation of the choline phosphate moiety in the hydrophilic head group of membrane lipid molecules, and the average structure and fluctuations of the fatty acids, which were mainly alkane chains in the hydrophobic part. In these structural studies, the goal was not to determine the predominant conformation of biomolecules, but to elucidate the average conformation of multiple conformers that were interchanging at high speed. We used physicochemical parameters to describe the changes in the average structure of lipid in membranes. Computational methods were adopted to estimate the structural changes in molecules, but experimental results are still important to judge the reliability of the calculation results. Through these studies, we discuss how the flexibility of biomolecules is involved in the expression of biological function.

Grafted Alkene Chains: Triggers for Defeating Contact Thermal Resistance in Composite Elastomers.

The pursuit of enhancing the heat transfer performance of composite elastomers as the thermal interface materials (TIMs) is a compelling and timely endeavor, given the formidable challenges posed by interfacial thermal transport in the domains of energy science, electronic technology, etc. Despite the efficacy of phase change materials (PCMs) in enhancing composite elastomers' interfacial compatibility, thereby reducing contact thermal resistance for heat transfer improvement, their leakage post-transition has impeded the widespread adoption of this approach. Herein, a strategy is proposed for developing a solid-solid phase change composite elastomer by grafting alkene chains onto the crosslink network to eliminate the possibility of leakage. A series characterization suggest that the resulting material possesses a self-adjusting interfacial compatibility feature to help reduce contact thermal resistance for heat transfer facilitating. The investigations on adhesion strength and surface energy reveal that the presence of amorphous grafted alkane chains at the interface facilitates easier absorption onto the contacting solid surface, enhancing intermolecular interactions at the interface to promote across-boundary heat transfer. By integrating these findings with the thermal performance evaluation of composite elastomers using a real test vehicle, valuable insights are gained for the design of composite elastomers, establishing their suitability as TIMs in relevant fields.

Effect of line tension on domain formation of fluorinated compounds at alkane/water interface

Condensed domain formation of fluorinated compounds (alcohol and ester) in adsorbed films at alkane/water interfaces was investigated by interfacial tensiometry, X-ray reflectometry, and BAM observation. The results obtained are explained by the effects of contact energy and dipole-dipole interaction, which are competitive contributions to the line tension acting at the domain boundary. Estimation of the two contributions indicated that the former is more dominant than the latter for the domain formation. In the adsorbed films of fluorinated alcohol, F8H2OH, at alkane/water interfaces, the domain formation was suppressed with increasing alkane chain length due to an increase in contact energy. The mixing of hybrid alcohol with fluorocarbon and hydrocarbon chains of the same carbon number, F6H6OH, in adsorbed film reduces contact energy. This stabilizes the dispersion of many domains with small size. On the other hand, when F8H2OH molecules are mixed with a cationic surfactant, C12TAB, in the adsorbed film, an attractive dipole-ion interaction between the hydrophilic groups relaxes the repulsive dipole-dipole interaction between F8H2OH molecules, resulting in the formation of domains with smooth boundary and large size. Furthermore, fluorinated ester, FC12Me molecules form flower shaped domains with intricate boundary mainly due to a larger dipole moment of FC12Me than F8H2OH.

Regulation of Nontraditional Intrinsic Luminescence (NTIL) in Hyperbranched Polysiloxanes by Adjusting Alkane Chain Lengths: Mechanism, Film Fabrication, and Chemical Sensing.

Biocompatible polymers with nontraditional intrinsic luminescence (NTIL) possess the advantages of environmental friendliness and facile structural regulation. To regulate the emission wavelength of polymers with NTIL, the alkane chain lengths of hyperbranched polysiloxane (HBPSi) are adjusted. Optical investigation shows that the emission wavelength of HBPSi is closely related to the alkane chain lengths; namely, short alkane chains will generate relatively long-wavelength emission. Electronic communication among functional groups is responsible for the emission. In a concentrated solution, HBPSi molecules aggregate together due to the strong hydrogen bond and amphiphilicity, and the functional groups in the aggregate are so close that their electron clouds are overlapped and generate spatial electronic delocalizations. HBPSi with shorter alkane chains will generate larger electronic delocalizations and emit longer-wavelength emissions. Moreover, these polymers show excellent applications in the fabrication of fluorescent films and chemical sensing. This work could provide a strategy for regulating the emission wavelengths of unconventional fluorescent polymers.

Distribution and abundance of oil-degrading bacteria in seawater of the Yellow Sea and Bohai Sea, China

Petroleum hydrocarbons are widespread in seawater. As an important sea area in northern China, the content and distribution of petroleum hydrocarbons in seawater need our attention because of the high toxicity and lasting polluting effects on the ecological environment of the Yellow Sea and Bohai Sea. In addition, there are few reports comparing the diversity of oil-degrading bacteria before and after enrichment. Therefore, we collected surface seawater from 10 sites in the Yellow Sea and Bohai Sea in the autumn of 2020 to study the distribution characteristics of total petroleum hydrocarbons (TPH) and the diversity of oil-degrading bacteria. The concentration of TPH was 81.65 μg/L-139.55 μg/L at ten sites in the Bohai Sea and the Yellow Sea, which conformed to the China Grade II water quality standard (GB3097–1997). Moreover, the pristine/phytane (PR/PH) value of most sites was close to 1, indicating that the area was obviously polluted by exogenous petroleum hydrocarbons. We found that oil-degrading bacteria in the seawater of the Yellow Sea and the Bohai Sea had a good degradation effect on C11-C14 short chain alkanes (degradation rate of 59.19–73.22 %) and C1-C4 phenanthrene (degradation rate of 48.19–60.74 %). In terms of the diversity of oil-degrading bacteria, Gammaproteobacteria and Alphaproteobacteria dominated the enriched bacterial communities. Notably, the relative abundance of Alcanivorax changed significantly before and after enrichment. We proposed that surface seawater in the Bohai Sea and Yellow Sea could form oil-degrading bacteria mainly composed of Alcanivorax, which had great potential for oil pollution remediation.

Kinetic study of hydrogen abstraction reactions from n-propyl/n-butylcyclohexane by hydrogen atom

Hydrogen abstraction reactions of alkylated cycloalkane by radicals play a fundamental role in combustion and atmospheric chemistry. In this work, we select two representative molecules in alkylated cycloalkane fuels, n-propylcyclohexane (nPCH) and n-butylcyclohexane (nBCH), to investigate the kinetics of their hydrogen abstraction reactions with hydrogen atom. The rate constants over a broad temperature range of 298–2000 K were calculated by using canonical transition state theory coupled with the multistructural torsional anharmonicity effect (TST/MS-T). We stress the particular importance of considering the MS-T anharmonicity for the investigated species involved in the H-abstraction pathways. Due to the approximate cancelation of the anharmonicity factor between the transition-state species and the reactant, the anharmonicity factors for reactions are spread over a narrower range of 0.7–3.3. The anharmonicity will slightly accelerate the H-abstraction for the nBCH system over the whole temperature range. The current results show that the multistructural torsional anharmonicity will influence the accurate estimation of competing relationships. We found that the total H-abstraction rate constants of the nBCH system by the TST/MS-T method are larger by factors of 1.2–1.3 than those for the nPCH system. The present data show that nPCH + H channels are less important by factors of 1.41–5.48 than currently estimated by the commonly used nPCH pyrolysis model. The H-abstraction ratios from the cyclic ring and side chain groups reveal that the rate rule for secondary carbon in chain alkanes does not represent the reactivity of all cycloalkanes well, e.g. the ratio between the cyclic ring and side chain group is high up to 2.8.

Adjusting effects of pyrolytic volatiles interaction in char to upgrade oil by swelling waste nylon-tire

Waste nylon-tire (WNT) is a typical solid municipal waste, pyrolysis efficiently disposes WNT to produce oil containing high-value chemicals. Upgrading the quality of oil is the key to improve WNT pyrolysis economy. Herein, swelling was applied to pretreat WNT, and swelled waste nylon-tire (SWNT) was pyrolyzed at different temperatures (400 °C–600 °C). Lower than 500 °C, swelling pretreatment realized the number of compounds in oil by GC–MS decreased 59.57% at 400 °C (60.78% at 450 °C, 67.97% at 500 °C) compared to Waste nylon-tire pyrolytic oil (TPO). Over 500 °C, this phenomenon weakened, decreased 47.67% at 550 °C (11.48% at 600 °C). At 400 °C and 450 °C, long chain methyl esters yield was over 30 A.% instead of short chain alkanes in TPO. D-limonene yield was over 20 A.% in oil of swelled waste nylon-tire (STPO). From 500 °C to 600 °C, swelling pretreatment affected the relative content of BTX and PAHs. At 500 °C and 550 °C, the relative content of BTX in STPO was more than twice of TPO, and BTX reached 28.75 A.% at 600 °C. PAHs in STPO appeared at 500 °C higher than TPO (450 °C), and PAHs was 0.73 A.% at 500 °C. Swelling pretreatment could produce more larger pores in particle during pyrolysis, which sharply inhibited the interaction of volatiles inside tire, so the number of compounds in oil sharply decreased at lower temperatures. Over 550 °C, temperature became the dominant role for generating oil, and components tended to be similar for STPO and TPO. CS2 with high-volatility released quickly from WNT during pyrolysis, it could be recycled to reduce final cost and environment impacts.

Microaerobic degradation of crude oil and long chain alkanes by a new Rhodococcus strain from Gulf of Mexico

Bacterial degradation of crude oil is a promising strategy for reducing the concentration of hydrocarbons in contaminated environments. In the first part of this study, we report the enrichment of two bacterial consortia from deep sediments of the Gulf of Mexico with crude oil as the sole carbon and energy source. We conducted a comparative analysis of the bacterial community in the original sediment, assessing its diversity, and compared it to the enrichment observed after exposure to crude oil in defined cultures. The consortium exhibiting the highest hydrocarbon degradation was predominantly enriched with Rhodococcus (75%). Bacterial community analysis revealed the presence of other hydrocarbonoclastic members in both consortia. In the second part, we report the isolation of the strain Rhodococcus sp. GOMB7 with crude oil as a unique carbon source under microaerobic conditions and its characterization. This strain demonstrated the ability to degrade long-chain alkanes, including eicosane, tetracosane, and octacosane. We named this new strain Rhodococcus qingshengii GOMB7. Genome analysis revealed the presence of several genes related to aromatic compound degradation, such as benA, benB, benC, catA, catB, and catC; and five alkB genes related to alkane degradation. Although members of the genus Rhodococcus are well known for their great metabolic versatility, including the aerobic degradation of recalcitrant organic compounds such as petroleum hydrocarbons, this is the first report of a novel strain of Rhodococcus capable of degrading long-chain alkanes under microaerobic conditions. The potential of R. qingshengii GOMB7 for applications in bioreactors or controlled systems with low oxygen levels offers an energy-efficient approach for treating crude oil-contaminated water and sediments.

A GC/C/IRMS-based method for position-specific carbon isotopic analysis of saturated long chain fatty acids

Intramolecular carbon isotope profiles (13C/12C) of mid- and long-chain saturated fatty acids represent a potentially rich source of pathway and flux information on fatty lipid biosynthesis. Accessing the PSIC-13C (position-specific carbon isotope composition) of saturated long chain fatty acids, however, proves a challenge as neither 13C NMR, nor online pyrolysis, can measure all carbons successfully. We have developed a wet chemistry procedure (α-bromination, α-hydrolysis and decarboxylation) to stepwise shorten the targeted saturated fatty acid, followed by GC/C/IRMS (gas chromatography/combustion/isotope ratio mass spectrometry) measurement of the 13C/12C ratios of fatty acids, with minimal purification. Isotope mass balance was then applied to calculate the 13C/12C ratios of individual carbons. The triplicated PSIA precision varies from position to position in the range 3.95–5.25 mUr (averaging 4.44 mUr, equivalent to ‰).Applying this method to a commercial C16:0 fatty acid of C3 botanical origin revealed an intramolecular odd-over-even 13C enrichment pattern, consistent with that obtained with 13C NMR. Although PSIA-13C was attempted only on a single fatty acid, the method can potentially be applied to obtain PISC-13C for all fatty acids in a mixture simultaneously, and to long chain saturated alkanes after proper functionalization. The method should prove useful in studies of lipid metabolism and biogeochemistry as both saturated long chain fatty acids and alkanes are the dominant organic archives of climate in petroleum deposits, sediments and soils.

Tuning catalyst performance in the SILP-catalyzed gas-phase hydroformylation of but-1-ene by choice of the ionic liquid

For the industrially relevant hydroformylation of but‑1-ene the concept of supported ionic liquid phase (SILP) has been applied previously. In this work, we have studied the influence of the type of ionic liquid (imidazolium and phosphonium based cations, various anions) on the solubility of the three reagents but‑1-ene, carbon monoxide and hydrogen. For the olefin, the predicted solubility values were determined using the COSMO-RS software tool. These data were compared to the experimentally determined values. A correlation between the predicted solubility and the observed activity within similar ILs could be observed. The highest activity could be obtained with the IL [N1888][NTf2]. A variation of the olefin chain length supported the observed correlation between solubility and activity. With increasing chain length, the activity of the SILP catalyst also increased. For the undesired consecutive reaction leading to aldols it was found that the substrate solubility does not significantly influence the activity or hydrocarbon accumulation under the used reaction conditions. The anion had a more pronounced effect on the accumulation of aldols, with hydrophilic Cl− and [EtOSO3]− showing lowest accumulation as well as aldol formation activity, while [NTf2]− showed highest values for both accumulation and formation activity. It was shown that the Kamlet-Taft-parameter β is a suitable value to be correlated with activity and accumulation for different ILs.

Influence of Base Oil Molecular Structure on the Tribological Performance of Diesel Engine Cylinder Liner and Piston Ring

Highly intensified diesel engines lead to severe lubricating condition, high performance lubricant is important to solve this problem. Base oil is the main composition of lubricant, which plays important role in lubricating performance. In this paper, three kinds of poly-α-olefin (PAO) base oil were prepared. Different olefin materials were used to produce PAO with different molecular structure. The tribological performance of diesel engine cylinder liner and piston ring lubricated with different base oil were evaluated by reciprocating test rig. Results show that PAO base oil synthesized with long carbon chain olefin has high viscosity index. The PC12 reduced the friction coefficient by 15.4%/19.6% in low speed/high speed friction compared with PC8. The wear of PC12 reduced 15.8% compared with PC8. The results were resulted from the long carbon chain of PC12, which produce high viscosity in high temperature and shear thin effect in high speed friction.

High-throughput bioamphiphile production by ethyl methane sulphonate induced mutant of hydrocarbonoclastic Enterobacter xiangfangensis STP-3: In depth structural elucidation and application to petroleum refinery oil sludge bioremediation

The environmental release of noxious petroleum hydrocarbons (PHCs) from the petroleum refining industries is an intractable global challenge. Indigenous PHCs degrading microbes produce insufficient yield of amphiphilic biomolecules with trivial efficiency makes the bioremediation process ineffective. In this concern, the present study is focused on the production of high yield multi-functional amphiphilic biomolecule through the genetic modification of Enterobacter xiangfangensis STP-3 strain using Ethyl methane sulphonate (EMS) induced mutagenesis. Mutant M9E.xiangfangensis showed 2.32-fold increased yield of bioamphiphile than wild-type strain. Novel bioamphiphile produced by M9E.xiangfangensis exhibited improved surface and emulsification activities which ensure the maximum degradation of petroleum oil sludge (POS) by 86% than wild-type (72%). SARA, FT-IR, and GC-MS analyses confirmed the expedited degradation of POS and ICP-MS analysis indicated the enhanced removal of heavy metals in connection with the ample production of functionally improved bioamphiphile. FT-IR NMR, MALDI-TOF, GC-MS and LC-MS/MS analyses portrayed the lipoprotein nature of bioamphiphile comprising pentameric fatty acid moiety conjugated with the catalytic esterase moiety. Further, homology modelling and molecular docking revealed the stronger interaction of hydrophobic amino acids, leucine and isoleucine with the PHCs in the case of wild-type esterase moiety, whereas in the mutant, aromatic amino acids were majorly interacted with the long chain and branched chain alkanes, thereby exhibited better efficiency. This is the first report on the adoption of EMS induced mutagenesis strategy to ameliorate the amphiphilic biomolecules for their sustainable applications in diverse biotechnological, environmental and industrial arenas.

Experimental and mechanistic study of bio-based solvent Cyrene for de-aromatization of model diesel

Liquid-liquid extraction is an important technique for separating aromatic and alkane hydrocarbons. The toxicity and pollution problems of traditional solvents are difficult to solve, and the use of green bio-based solvents for diesel fuel dearomatization is of great significance to solve energy and environmental problems. In this paper, Cyrene, a low toxicity, low cost, green composition bio-based solvent, was selected as an extractant to study its ability to remove mono- and bicyclic aromatics from chain alkanes and cycloalkanes, respectively. In addition to the ternary system, the extraction effects under various experimental conditions and multi-component simulated systems were also investigated. The results showed that aromatics and cyclic structures tend to interact more strongly with Cyrene due to differences in solute structure, and therefore polycyclic aromatic hydrocarbons tend to produce larger distribution coefficients. the selectivity coefficients of Cyrene for the four systems were influenced by differences in interaction energies in the order: dodecane/1-methylnaphthalene > dodecane/indene > decahydronaphthalene/1-methylnaphthalene > decahydronaphthalene/indene. At the same time, multi-component simulated oil experiments have demonstrated that Cyrene is equally selective in removing aromatic hydrocarbons from complex components. Quantum chemical calculations were used to investigate the extraction mechanism of Cyrene. The results of Reduced Density Gradient (RDG), Atoms In Molecules (AIM), and Symmetry-Adapted Perturbation Theory (SAPT) energy decomposition proved that the interaction forces between Cyrene and solute molecules are van der Waals forces dominated by dispersion forces and accompanied by some very weak hydrogen bonds. Finally, thermodynamic correlations using the NRTL model were performed to obtain binary interaction parameters for the four systems. The results of this paper indicate that Cyrene, as a new green bio-based solvent, has the potential to be used as an extractant and shows good separation in the removal of long carbon chain aromatic hydrocarbons, and this paper also provides basic data and references for subsequent studies.

A highly sensitive electrochemical sensor derived from peptide amphiphilic inspired self-assembled, ordered gold nanoparticles for determination of 22 β-lactams

Achieving ordered arrangement of gold nanoparticles (AuNPs) on an electrode can further improve the signal intensity of an electrochemical immunosensor. This ordered AuNPs self-assembly can be inspired by peptide amphiphile (PA). The rational design of hydrophobic chains in PA is a crucial step when the range of hydrophobic alkane chain from 14 to 18 carbons. As arginine (R) can combine specifically with Au surface plane (111), four PAs, i.e., C15H23CO-RR (C16R2), C15H23CO-RRR (C16R3), C15H23CO-RRRR (C16R4), and C15H23CO-RRRRR (C16R5), in this work are designed to investigate the extent of ordered AuNPs self-assembly. The results indicate that C16R4 presented a dominant electron donating ability and can inspire the self-assembly of AuNPs to form a mono-dispersed raspberry-like structure (C16R4-AuNPs) to obtain the largest ΔI (15.4 μA). In the detection system, C16R4-AuNPs firstly capture and immobilize anti-β-lactam receptor monoclonal antibodies (mAb) by electrostatic adsorption, and the anti-β-lactam receptor mAb possess antigen-antibody binding sites away from the active site of the receptors. Then, they capture β-lactam receptors through an antigen-antibody reaction to form a ternary complex (C16R4-AuNPs-mAb-β-lactam receptors). Based on this indirect-labeling process, the receptor active sites have been exposed completely, facilitating ligand recognition, which greatly further improves the sensitivity of the present method. Finally, a highly sensitive electrochemical immunosensor based on the ternary complex is developed to achieve the determination of 22 β-lactam antibiotics, which is more sensitive and applicable than other reported electrochemical sensors.

Novel Anionic-Nonionic Surfactant Based on Water-Solid Interfacial Wettability Control for Residual Oil Development.

Irreversible colloidal asphaltene adsorption layers are formed on formation rock surfaces due to long-term contact with crude oil, and large amounts of crude oil adhere to these oil-wet layers to form residual oil films. This oil film is difficult to peel off due to the strong oil-solid interface effect, which seriously restricts further improvement in oil recovery. In this paper, the novel anionic-nonionic surfactant sodium laurate ethanolamide sulfonate (HLDEA) exhibiting strong wetting control was synthesized by introducing sulfonic acid groups into the nonionic surfactant laurate diethanolamide (LDEA) molecule through the Williamson etherification reaction. The introduction of the sulfonic acid groups greatly improved the salt tolerance and the absolute value of the zeta potential of the sand particles. The experimental results showed that HLDEA altered the wettability of the rock surface from oleophilic to strongly hydrophilic, and the underwater contact angle increased substantially from 54.7 to 155.9°. In addition, compared with LDEA, HLDEA exhibited excellent salt tolerance and enhanced oil recovery performance (the oil recovery was improved by 19.24% at 2.6 × 104 mg/L salinity). Based on nanomechanical experimental results, HLDEA was efficiently adsorbed on the core surfaces and regulated microwetting. Moreover, HLDEA effectively reduced the adhesion force between the alkane chains and the core surface, which facilitated residual oil stripping and oil displacement. This new anionic-nonionic surfactant affording great oil-solid interface wetting control has practical significance for the efficient development of residual oil.

The Transport of Charged Molecules across Three Lipid Membranes Investigated with Second Harmonic Generation.

Subtle variations in the structure and composition of lipid membranes can have a profound impact on their transport of functional molecules and relevant cell functions. Here, we present a comparison of the permeability of bilayers composed of three lipids: cardiolipin, DOPG (1,2-dioleoyl-sn-glycero-3-phospho-(1'-rac-glycerol), and POPG (1-palmitoyl-2-oleoyl-sn-glycero-3-phospho-(1'-rac-glycerol)). The adsorption and cross-membrane transport of a charged molecule, D289 (4-(4-diethylaminostyry)-1-methyl-pyridinium iodide), on vesicles composed of the three lipids were monitored by second harmonic generation (SHG) scattering from the vesicle surface. It is revealed that structural mismatching between the saturated and unsaturated alkane chains in POPG leads to relatively loose packing structure in the lipid bilayers, thus providing better permeability compared to unsaturated lipid bilayers (DOPG). This mismatching also weakens the efficiency of cholesterol in rigidifying the lipid bilayers. It is also revealed that the bilayer structure is somewhat disturbed by the surface curvature in small unilamellar vesicles (SUVs) composed of POPG and the conical structured cardiolipin. Such subtle information on the relationship between the lipid structure and the molecular transport capability of the bilayers may provide clues for drug development and other medical and biological studies.

Insight into the mechanisms for pyrolyzing organic macromolecular structure of subbituminous coal by comparing the extraction and flash pyrolysis

Investigating the organic structure of coal is an essential basic research for producing clean fuels and value-added fine chemicals by the clean and efficient utilization of coal. As a consequence, the structural characteristics of organic macromolecular in subbituminous coal (SBC) were analyzed at different levels using multiple destructive and non-destructive technical strategies. Correspondingly, the pyrolysis mechanisms of SBC organic macromolecular structure were investigated to understand through the molecular level correlation group component from extraction portion (EP) and flash pyrolysis (FP). In detail, solid-state 13C nuclear magnetic resonance analysis indicates that carbon skeleton of SBC mainly consists of aliphatic carbons (48.5%) and aromatic carbons (50.3%). The number of substituents on each aromatic ring in SBC is up to 2 on average and aliphatic linkages connect 3–4 aromatic rings. X-ray photoelectron spectrometer analysis exhibits that the >C–O- groups, pyrrolic, and sulfonic sulfurs of organic components are the most abundance O-, N-, and S-containing species, which is consistent with Fourier transform infrared and solid-state 13C nuclear magnetic resonance. The destructive analysis with thermogravimetric implies that organic macromolecular structure in SBC consists different types of covalent bonds (>Cal-X) with different strength. Furthermore, the contents of chain alkanes (CAs, 17.4%), arenes (62.7%), and oxygen-containing organic species (OCOSs, 18.0%) in EP from SBC (EPSBC), while the CAs (53.1%), alkenes (7.4%), arenes (27.3%), and OCOSs (7.5%) in FP of SBC (FPSBC). Comprehensive comparative analysis of detectable small molecule species from EPSBC and FPSBC further indicate that the cleavage > Cal-X bridge bonds of organic macromolecular structure in SBC attack by active hydrogen (H‧) through the pyrolysis reaction to obtain more alkenes, CAs, alkanols, and phenols.

ANALYSIS OF THE COMPOSITION AND STRUCTURE OF HEAVY OILS ACCORDING TO NMR SPECTROSCOPY

The results of studies of 1H and 13C NMR spectroscopy of heavy oil samples from the Timan Pechersk, Volga Ural oil and gas basins are presented. Knowledge of the chemical composition and physicochemical properties of crude oil, along with the particularities of geological and geochemical conditions is of paramount importance for solving the problems of the origin of crude oil and its subsequent processing. Information on the chemical composition of oil allows you to combine samples of crude oil from various fields before refining to achieve the necessary commercial and technical characteristics. 59.7-60.5% of β-CH3 groups were found in the samples, in β-CH2 and CH-groups to the aromatic ring, as well as the content of CH2- and CH-groups of saturated compounds. Dividing 13C NMR spectra into ranges shows a high content of methyl groups with the number of CH-groups in the alkyl fragments and CH and CH2-alkyl groups of naphthenic moieties attached to CH-group being 14.37-24.17%. A specific range of values is from 9.4 to 11.4 ppm. indicates methyl substituted octane, nonane or decane. It was found that the content of primary and secondary carbon atoms was in the range from 59.4-60.7%. The studied samples possess branched alkane chains. Comparison of the content of aromatic / aliphatic components allows us to determine the sample of the Volga Ural basin as a sample with a high content of aromatic component. The content of aromatic fragments varies in a wider range of 17-25.9%. From the data of 1H NMR-spectra of samples of heavy oils with different origin, viscosity and treatment it was found that crude and refined oils can differ in the content of olefin signals. For citation: Kolchina G.Yu., Poletaeva O.Yu., Leontev A.Yu., Movsumzade E.M., Loginova M.E., Kolchin A.V. Analysis of the composition and structure of heavy oils according to NMR spectroscopy. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2023. V. 66. N 6. P. 94-101. DOI: 10.6060/ivkkt.20236606.6783.