Synthesis of straight-chain C_(49)H_(100) alkane using a modular splicing strategy

Ultra-long n-alkanes are highly valuable in both scientific research and as major constituents of specialty high-melting-point waxes.Unlike conventional methods(e.g.,Fischer–Tropsch(FT),ethylene oligomerization,and polyethylene cracking)typically resulting in wide n-alkane distributions,the elaborate design strategy presented herein allows the direct synthesis of pure,long n-alkanes using a modular splicing method with acetone,furfural,and fatty acid anhydrides or acyl chlorides as bio-blocks.The herein approach is based on a simple four-step catalytic reaction scheme involving C–C chain elongation and C–O bond activation.The synthesized pure n-alkanes had a carbon chain length as high as C_(49)(total yield of 49%).The synthesis approach also allows to selectively prepare n-alkanes with even and odd carbon numbers ranging from C15 to C_(49).This process represents a great breakthrough in the synthesis of long-chain pure n-alkanes,surpassing the carbon number limitations reported in previous methodologies.

Characteristics of carbon isotopic composition of alkane gas in large gas fields in China

Exploration and development of large gas fields is an important way for a country to rapidly develop its natural gas industry.From 1991 to 2020,China discovered 68 new large gas fields,boosting its annual gas output to 1925×108m3in 2020,making it the fourth largest gas-producing country in the world.Based on 1696 molecular components and carbon isotopic composition data of alkane gas in 70 large gas fields in China,the characteristics of carbon isotopic composition of alkane gas in large gas fields in China were obtained.The lightest and average values ofδ^(13)C_(1),δ13C2,δ13C3andδ13C4become heavier with increasing carbon number,while the heaviest values ofδ^(13)C_(1),δ13C2,δ13C3andδ13C4become lighter with increasing carbon number.Theδ^(13)C_(1)values of large gas fields in China range from-71.2‰to-11.4‰(specifically,from-71.2‰to-56.4‰for bacterial gas,from-54.4‰to-21.6‰for oil-related gas,from-49.3‰to-18.9‰for coal-derived gas,and from-35.6‰to-11.4‰for abiogenic gas).Based on these data,theδ^(13)C_(1)chart of large gas fields in China was plotted.Moreover,theδ^(13)C_(1)values of natural gas in China range from-107.1‰to-8.9‰,specifically,from-1071%o to-55.1‰for bacterial gas,from-54.4‰to-21.6‰for oil-related gas,from-49.3‰to-13.3‰for coal-derived gas,and from-36.2‰to-8.9‰for abiogenic gas.Based on these data,theδ^(13)C_(1)chart of natural gas in China was plotted.

Low molecular weight alkane-fed solid oxide fuel cells for power and chemicals cogeneration

This paper presents a review of low molecular weight alkane-fed solid oxide fuel cells(SOFCs),which,unlikely the conventional use of SOFCs for only power production,are utilized to cogenerate produce useful chemicals at the same time.The cogeneration processes in SOFC have been classified according to the different types of fuel.C_(2)and C_(3)alkenes and synthesis gas are the main cogenerated chemicals together with electricity.The chemicals and energy cogeneration in a fuel cell reactor seems to be an effective alternative to conventional reactors for only chemicals production and conventional fuel cells for only power production.Although,the use of SOFCs for chemicals and energy cogeneration has proved successful in the industrial setting,the development of new catalysts aimed at obtaining the desired chemicals together with the production of a high amount of energy,and optimizing SOFC operation conditions is still a challenge to enhance system performance and make commercial applications workable.

Structural characterization and mass spectrometry fragmentation signatures of macrocyclic alkanes isolated from a Sydney Basin torbanite,Australia

Individual hydrocarbons identified to be macrocyclic alkanes in a torbanite from the Sydney Basin(Australia)were successfully isolated from its extracts using preparative gas chromatography and analyzed by NMR.Saturated cyclic structures were confirmed by single peaks in the NMR~1H and~(13)C spectra indicating single forms of H and C atoms exist in these biomarker molecules.This is consistent with the methylene unit in a ring system assignment of the macrocyclic alkanes and accounts for a formula of(CH2)n.The unusual molecular structures of these compounds are consistent with those that were identified from previous GC retention index data and co-injection with a standard supports the previous research.The mass spectral fragmentation behaviors of representative cyclic alkanes were further investigated by comparing them with the mass spectra of isolated individual macrocyclic alkanes.The characteristic fragment ions in the macrocyclic alkanes of(M–28)+and base peaks of m/z 97,111,125,etc.,can be assigned as being generated by simple a-/i-cleavage and hydrogen rearrangement.These fragmentation pathways combined with retention indices should assist in differentiating these compounds from monounsaturated alkenes and alkylated monocyclics having similar mass spectral characteristics in other geological samples.

Challenges and opportunities in plasma-activated reactions of CO_(2) with light alkanes

Mitigation of the deleterious environmental impacts associated with CO_(2) emissions requires the development of more sustainable processes for synthesizing fuels and chemicals.Selective conversion of abundant yet difficult to activate molecules such as CO_(2) and surplus light alkanes from shale gas to desirable products can potentially reduce reliance upon conventional fossil-based feedstocks.Therefore,co-conversion of CO_(2) with abundant light alkanes such as methane and ethane using atmospheric-pressure.

Even-carbon predominance of Monomethyl branched alkanes in Humic coal from Junggar Basin,NW China

A series of Monomethyl branched alkanes compounds were detected between nC14-nC36,in immature and low maturity Jurassic humic coal,Junggar basin.2-methyl alkanes and 3-methyl alkanes accounted for the vast majority of the compounds.It is worth noting that the2-methyl alkanes in the humic coal samples show an obvious distribution of even carbon predominances rarely reported in the literature.The results show that with the increase of Pr/Ph(pristane/phytane),the even carbon dominance of 2-methyl alkanes is more obvious,while the odd carbon number distribution of 3-methyl alkanes is weakened.As Pr/Ph increases in the humic coal,the relative content of the hopanes increased,while the relative content of 2-methyl alkanes and 3-methyl alkanes increases first and then decreases.

Zinc-modified Pt/SAPO-11 for improving the isomerization selectivity to dibranched alkanes

Zinc-modified Pt/SAPO-11 catalysts were prepared by incipient wetness impregnation and assessed in the hydroisomerization of n-octane.Their physicochemical properties were investigated using powder X-ray diffraction,scanning electron microscopy,nitrogen adsorption-desorption,pyridine-adsorbed infrared spectroscopy,temperature-programmed desorption of NH3,temperature-programmed reduction of hydrogen,temperature-programmed desorption of hydrogen,transmission electron microscopy,and X-ray photoelectron spectroscopy.The addition of zinc resulted in high dispersion of platinum.Zinc acted as a competitive adsorbent,changed the location of platinum.The catalyst with a zinc loading of 0.5%gave the highest selectivity to dimethylhexanes,but the conversion was lower than those achieved with the other catalysts.Dimethylhexanes have large molecular diameters,and therefore their diffusion may be difficult.This weakens the catalytic activity of the zinc-modified catalysts and lowers the n-octane conversion.

Analysis of the Alkane Hydroxylase Gene and Long-Chain Cyclic Alkane Degradation in <i>Rhodococcus</i>

To characterize the long-chain cyclic alkane (c-alkane) degradation of bacteria in Rhodococcus, we analyzed the relationship between the alkane hydroxylase gene (alkB) and long-chain c-alkane degradation in 19 species. Eleven strains which were isolated from nature using long-chain c-alkane as a substrate were identified as R. erythropolisc, and all were shown to carry the alkB [alkB R2 type]. This gene type was also carried by two other species, R. rhodochrous and R. baikonurensis. In total, 17 species of the genus Rhodococcus carried alkB, but the gene types differed from each other. The two species R. rhodnii and R. coprophilus did not carry alkB, and their long-chain c-alkane degradation levels were low.

Ni-based catalysts derived from a metal-organic framework for selective oxidation of alkanes

Ni nanoparticles embedded in nitrogen-doped carbon（Ni@C-N） materials were prepared by ther-molysis of a Ni-containing metal-organic framework （Ni-MOF） under inert atmosphere. The as-synthesized Ni@C-N materials were characterized by powder X-ray diffraction, N_2 adsorp-tion-desorption analysis, scanning electron microscopy, transmission electron microscopy, atomic absorption spectroscopy, and X-ray photoelectron spectroscopy. The MOF-derived Ni-based mate-rials were then examined as heterogeneous catalysts for the oxidation of alkanes under mild reac-tion conditions. The Ni@C-N composites displayed high activity and selectivity toward the oxidation of a variety of saturated C–H bonds, affording the corresponding oxidation products in good-to-excellent yields. Furthermore, the catalysts could be recycled and reused for at least four times without any significant loss in activity and selectivity under the investigated conditions.

Computer-aided ionic liquid design for alkane/cycloalkane extractive distillation process

A computer-aided ionic liquid design(CAILD) study is presented for the frequently encountered alkane/cycloalkane separations in petrochemical industry. Exhaustive experimental data are first collected to extend the UNIFAC-IL model for this system, where the proximity effect in alkanes and cycloalkanes is considered specifically by defining distinct groups. The thermodynamic performances of a large number of ILs for 4 different alkane/cycloalkane systems are then compared to select a representative example of such separations. By applying n-heptane/methylcyclohexane extractive distillation as a case study, the CAILD task is cast as a mixed-integer nonlinear programming(MINLP) problem based on the obtained task-specific UNIFAC-IL model and two semi-empirical models for IL physical properties. The top 5 IL candidates determined by solving the MINLP problem are subsequently introduced into Aspen Plus for process simulation and economic analysis, which finally identify 1-hexadecyl-methylpiperidinium tricyanomethane([C_(16)MPip][C(CN)_3]) as the best entrainer for this separation.

A viewpoint on catalytic origin of boron nitride in oxidative dehydrogenation of light alkanes

Oxidative dehydrogenation of light alkanes to alkenes is an attractive alternative route for industrial direct dehydrogenation because of favorable thermodynamic and kinetic characteristics,but encounters difficulties in selectivity control for alkenes because of over-oxidation reactions that produce a substantial amount of undesired carbon oxides.Recent progress has revealed that boron nitride is a highly promising catalyst in the oxidative dehydrogenation of light alkanes because of its superior selectivity for and high productivity of light alkenes,negligible formation of CO2,and remarkable catalyst stability.From this viewpoint,recent works on boron nitride in the oxidative dehydrogenations of ethane,propane,butane,and ethylbenzene are reviewed,and the emphasis of this viewpoint is placed on discussing the catalytic origin of boron nitride in oxidative dehydrogenation reactions.After analyzing recent progress in the use of boron nitride for oxidative dehydrogenation reactions and finding much new evidence,we conclude that pure boron nitride is catalytically inert,and an activation period is required under the reaction conditions;this process is accompanied by an oxygen functionalization at the edge of boron nitride;the B-O species themselves have no catalytic activity in C-H cleavage,and the B-OH groups,with the assistance of molecular oxygen,play the key role in triggering the oxidative dehydrogenation of propane;the dissociative adsorption of molecular oxygen is involved in the reaction process;and a straightforward strategy for preparing an active boron nitride catalyst with hydroxyl groups at the edges can efficiently enhance the catalytic efficacy.A new redox reaction cycle based on the B-OH sites is also proposed.Furthermore,as this is a novel catalytic system,there is an urgent need to develop new methods to optimize the catalytic performances,clarify the catalytic function of boron species in the alkane ODH reactions,and disclose the reaction mechanism under realistic reaction conditions.

Electrospinning synthesis of porous boron-doped silica nanofibers for oxidative dehydrogenation of light alkanes

The discovery of the high activity and selectivity of boron-based catalysts for oxidative dehydrogenation(ODH)of alkanes to olefins has attracted significant attention in the exploration of a new method for the synthesis of highly active and selective catalysts.Herein,we describe the synthesis of porous boron-doped silica nanofibers(PBSNs)100-150 nm in diameter by electrospinning and the study of their catalytic performance.The electrospinning synthesis of the catalyst ensures the uniform dispersion and stability of the boron species on the open silica fiber framework.The one-dimensional nanofibers with open pore structures not only prevented diffusion limitation but also guaranteed high catalytic activity at high weight hourly space velocity(WHSV)in the ODH of alkanes.Compared to other supported boron oxide catalysts,PBSN catalysts showed higher olefin selectivity and stability.The presence of Si-OH groups in silica-supported boron catalysts may cause low propylene selectivity during the ODH of propane.When the ODH conversion of ethane reached 44.3%,the selectivity and productivity of ethylene were 84%and 44.2%g_(cat)^(-1)s^(-1),respectively.In the case of propane ODH,the conversion,selectivity of olefins,and productivity of propylene are 19.2%,90%,and 76.6 jimol g_(cat)^(-1)s^(-1),respectively.No significant variations in the conversion and product selectivity occurred during 20 h of operation at a high WHSV of 84.6 h^(-1).Transient analysis and kinetic experiments indicated that the activation of O2 was influenced by alkanes during the ODH reaction.

Constant Volume Spray Auto-ignition Study of Alkanes

Spray auto-ignition experiments were carried out in a constant volume combustion chamber for some pure alkanes(n-paraffins with different chain length, cyclohexane, n-butyl cyclohexane, and isooctane) and blends of n-decane with Standard Blended Fuel(isooctane/n-heptane) and product gasoline. Test results showed that the reaction activity of n-paraffins was relatively high. Meanwhile, the auto-ignition characteristics differed significantly with the molecular structures of alkanes. Adding different volume fractions of n-decane to Standard Blended Fuel and product gasoline could improve the fuel reaction activity at varying degree. Finally, functional groups effects were used to simulate the relationship between the molecular topology and the auto-ignition quality.

A Quantitative Structure Property Relationship for Prediction of Flash Point of Alkanes Using Molecular Connectivity Indices

Many structure-property/activity studies use graph theoretical indices, which are based on the topological properties of a molecule viewed as a graph. Since topological indices can be derived directly from the molecular structure without any experimental effort, they provide a simple and straightforward method for property prediction. In this work the flash point of alkanes was modeled by a set of molecular connectivity indices （Х）, modified molecular connectivity indices （ ^mХ^v ） and valance molecular connectivity indices （ ^mХ^v ）, with ^mХ^v calculated using the hydrogen perturbation. A stepwise Multiple Linear Regression （MLR） method was used to select the best indices. The predicted flash points are in good agreement with the experimental data, with the average absolute deviation 4.3 K.

Enthalpies Estimation of Formation of Monosubstituted Alkanes by Interaction Potential Index

The interaction potential index IPI（X） of 16 Br, C1, I, NO2, CN, CHO, COOH, CH3, CH： kinds of substituents X （X---OH, SH, NH2, ：CH2, C-CH, Ph, COCH3, COOCH3） were proposed, which are derived from the experimental enthalpies of formation △fHФ （g） values of monosubstituted straight-chain alkanes. Based on the IPI（X） and polarizability effect index, a simple and effective model was constructed to estimate the △fHФ （g） values of monosubstituted alkanes RX （including the branched derivatives）. The present model takes into account not only the contributions of the alkyl R and the substituent X, but also the contribution of the interaction between R and X. Its stability and prediction ability was confirmed by the results of leave-one-out method. Compared with previous reported studies, the obtained equation can be used to estimate enthalpies of formation for much more kinds of monosubstituted alkanes with less parameters. Thus, it is recommended for the calculation of the △fHФ（g） for the RX.

Predicting hydrate forming pressure of pure alkanes in the presence of inhibitors

An inherent problem with natural gas production or transmission is the formation of gas hydrates, which can lead to safety hazards for production/transportation systems, and substantial economic risks. Hydrate inhibition with different inhibitors such as, methanol, ethylene glycol （EG）, triethylene glycol （TEG）, and sodium chloride solution continues to play a critical role in many operations. An understanding of when the hydrates form in the presence of these hydrate inhibitors, is therefore necessary to overcome hydrate problems. Several thermodynamic models have been proposed for predicting the hydrate formation conditions in aqueous solutions containing methanol/glycols and electrolytes. However, available models have limitations that include the types of liquid, compositions of fluids, and inhibitors used. The aim of this study is to develop a simple-to-use correlation for accurate prediction of hydrate-forming pressures of pure alkanes in the presence of different hydrate inhibitors, where the obtained results illustrate good agreement with the reported experimental data.

Recent Results on Fast Flow Gas-Phase Partial Oxidation of Lower Alkanes

Recent experimental results and kinetic modeling of fast flow gas-phase oxidation of methane and other lower alkanes to methanol and other oxygenates are discussed, alongside with prospects and possible areas for applications of the processes.

Heterogeneous catalytic partial oxidation of lower alkanes(C_1–C_6) on mixed metal oxides

This review paper aims at analysing the state of the art for partial oxidation and oxidative dehydrogenation（ODH） reactions of lower alkanes C–Cinto olefins and oxygenated products（aldehydes, anhydrides,carboxylic acids） on metal oxide catalysts with cations of variable oxidation state, such as Mo and V in particular. Key parameters to be met by the catalysts, such as their redox properties, their structural aspects, active sites composed of ensembles of atoms isolated one from the others, mechanisms of reactions, are discussed. Main features of the different reactions of C–Calkanes and catalysts are analysed and their generalisation for determining more active and more selective catalysts is attempted. Prospective views for the future of the domain are proposed.

Geochemical characteristics of abiogenic alkane gases

Recently abiogenic alkanes have been found in various locations in the world and other celestial bodies. The chemical composition of abiogenic alkane gases varies widely. The content of methane is low and nearly no C2+ is found in the abiogenic alkane gases from fluid inclusions in volcanic rocks or hot springs in China. In the unsedimented submarine hydrothermal vent system C1/C2+ ratios are much greater than those for the thermogenic gases, mostly >800 and in some cases up to 8,000. In the Songliao Basin, China, C1/C2+ of some abiogenic gases are often less than 150. Abiogenic alkane gases which have been found in nature often have carbon isotopic reversal among C1–C4 alkanes (δ13C1>δ13C2>δ13C3>δ13C4), whereas both regular and reversed hydrogen isotope distribution pattern among C1–C4 alkanes have been reported. The δ13C of abiogenic methane is mainly greater than ?30‰ though laboratory synthesized methane can have δ13C as low as ?57‰, and its δD1 values vary widely and overlap with biogenic gases. High 3He/4He ratios often indicate the addition of mantle-derived helium and are related to abiogenic gases. However, some biogenic gases can also have high 3He/4He ratios up to 8. The CH4/3He end-member is often lower than 106 for abiogenic alkane gases while greater than 1013 for biogenic gases, and the values between these two end-members often reflect the mixing of biogenic and abiogenic gases.

SbCl_3 Catalyzed Solventless Synthesis of Bis(indolyl)alkanes under Grinding

A clean and efficient method for the synthesis of bis（indolyl）alkanes with antimony trichloride（SbCl3） as the catalyst under solvent-free grinding conditions is described. This method provides several advantages, such as simple work-up procedure, neutral conditions and high yields.