The efficient hydrogenolysis of esters to alkanes is the key protocol for producing advanced biofuels from renewable plant oils or fats.Due to the low reactivity of the carbonyl group in esters,a high reaction tempera...The efficient hydrogenolysis of esters to alkanes is the key protocol for producing advanced biofuels from renewable plant oils or fats.Due to the low reactivity of the carbonyl group in esters,a high reaction temperature(>250℃)is the prerequisite to ensure high conversion of esters.Here,we report a highly dispersed MoO_(x)-Ru/C bimetallic catalyst for the efficient hydrogenolysis of esters to alkanes under 150°C.The optimal catalyst exhibits>99%conversion of methyl stearate and 99%selectivity to diesel-range alkanes,reaching a high rate of up to 2.0 mmol gcat^(–1)h^(–1),5 times higher than that of Ru/C catalyst(MoO_(x)/C is inert).Integrated experimental and theoretical investigations attribute the high performance to the abundant MoO_(x)-Ru interfacial sites on the catalyst surface,which offers high activity for the C–O cleavage of esters.Furthermore,the dispersed MoO_(x)species significantly weaken the hydrocracking activity of the metallic Ru for C–C bonds,thus yielding alkane products without carbon loss.This study provides a facile and novel strategy for the design of high-performance heterogeneous catalysts for the hydrodeoxygenation of biomass-derived esters to alkane products.展开更多
Aromatization of light alkanes is a value-added process in both petrochemical and coal chemical industries.Here,single[Ga(OH)]^(2+)ion-exchanged mesoporous hollow-structured ZSM-5(Ga-MH-ZSM-5)material was prepared,and...Aromatization of light alkanes is a value-added process in both petrochemical and coal chemical industries.Here,single[Ga(OH)]^(2+)ion-exchanged mesoporous hollow-structured ZSM-5(Ga-MH-ZSM-5)material was prepared,and it shows unprecedented catalytic performance in light alkane aromatization,considering activity,product selectivity and catalytic stability.The average aromatics yields in ethane aromatization at 600℃and WHSV of 0.8 h^(-1) within 28 h and in propane aromatization at 580℃and WHSV of 1.1 h^(-1) within 20 h reach~18.4%and~70.8%with benzene,toluene and xylenes(BTX)accounting for~96%and~88%of aromatics,respectively.Ga-MH-ZSM-5-0.41 gave a TON for formation of aromatics(TON_(aromatics))from propane as high as 57479,whereas the reported catalysts maximally show a TON_(aromatics) of 5514.This also holds true for ethane aromatization;the TON_(aromatics) obtained on Ga-MH-ZSM-5-0.41 was³3845 in contrast to£392 on reported non-noble metal catalysts.The catalytic activity of Ga-MH-ZSM-5 highly depends on Ga species structures.[Ga(OH)]^(2+)ions are predominant species at Ga loading≤0.3 wt%,while more[Ga(OH)_(2)]^(+)and GaO_(x) oligomers are formed with increasing Ga content.Upon reduction with H_(2),[Ga(OH)]^(2+)and[Ga(OH)_(2)]^(+)are transformed into[GaH]^(2+)and[GaH_(2)]^(+)species,which show a propane dehydrogenation rate of 300 and 15 times of that of Brønsted acid sites respectively.The light alkanes are mainly dehydrogenated into light olefins on[GaH]^(2+)species,and then,oligomerized and cyclized into(alkyl)cycloalkanes on H^(+)sites,which is followed by possible ring expansion on H^(+)and sequential dehydrogenations into aromatics primarily on[GaH]^(2+).展开更多
To achieve palm oil conversion along with a high yield of long‐chain alkane,a series of NiFe layered double oxide catalysts were prepared and employed in the deoxygenation of palm oil.The layered structure of these c...To achieve palm oil conversion along with a high yield of long‐chain alkane,a series of NiFe layered double oxide catalysts were prepared and employed in the deoxygenation of palm oil.The layered structure of these catalysts was confirmed by XRD and SEM analyses,and Ni and Fe species existed primarily in the forms of Ni^(2+)and Fe^(3+),respectively.It was found that Ni/Fe molar ratio influenced the H_(2)reducibility and surface properties of NiFe catalysts.Specifically,Ni_(2)Fe‐LDO and Ni_(3)Fe‐LDO exhibited higher reducibility under H_(2)atmosphere.Moreover,the Ni_(2)Fe‐LDO catalyst contained a higher concentration of surface oxygen species(Osurf).Deoxygenation results demonstrated that the Ni_(2)Fe‐LDO catalyst achieved superior palm oil conversion,higher liquid product yield and enhanced selectivity toward C_(15)–C_(18)hydrocarbons compared to other catalysts.This improved performance was attributed to its higher hydrogen dissociation activity and enhanced adsorption capacity for palm oil molecules.Furthermore,reaction condition studies revealed that palm oil was completely converted,yielding 86.8%liquid product with 81.8%selectivity of C_(15)–C_(18)hydrocarbons at 350℃under 7 MPa H_(2)pressure.This finding provides an insight into the development of efficient catalysts for the deoxygenation of fatty compounds to biofuels.展开更多
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,s...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.展开更多
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...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.展开更多
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...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.展开更多
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 we...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.展开更多
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 UN...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.展开更多
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 synthe...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.展开更多
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...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.展开更多
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-...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.展开更多
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 experimenta...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.展开更多
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 t...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.展开更多
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 molecul...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.展开更多
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 inhibit...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.展开更多
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 appl...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.展开更多
An efficient synthetic method for bis（indol-3-yl）alkane derivatives has been developed.In the presence of 5 mol%of pyridinium tribromide（PTB）,the condensation of indoles and aldehydes proceeded smoothly under mild...An efficient synthetic method for bis（indol-3-yl）alkane derivatives has been developed.In the presence of 5 mol%of pyridinium tribromide（PTB）,the condensation of indoles and aldehydes proceeded smoothly under mild conditions,giving rise to the corresponding bis（indol-3-yl）alkanes in good to excellent yields.展开更多
Light olefins are important platform feedstocks in the petrochemical industry,and the ongoing global economic development has driven sustained growth in demand for these compounds.The dehydrogenation of alkanes,derive...Light olefins are important platform feedstocks in the petrochemical industry,and the ongoing global economic development has driven sustained growth in demand for these compounds.The dehydrogenation of alkanes,derived from shale gas,serves as an alternative olefins production route.Concurrently,the target of realizing carbon neutrality promotes the comprehensive utilization of greenhouse gas.The integrated process of light alkanes dehydrogenation and carbon dioxide reduction(CO_(2)-ODH)can produce light olefins and realize resource utilization of CO_(2),which has gained wide popularity.With the introduction of CO_(2),coke deposition and metal reduction encountered in alkanes dehydrogenation reactions can be effectively suppressed.CO_(2)-assisted alkanes dehydrogenation can also reduce the risk of potential explosion hazard associated with O_(2)-oxidative dehydrogenation reactions.Recent investigations into various metal-based catalysts including mono-and bi-metallic alloys and oxides have displayed promising performances due to their unique properties.This paper provides the comprehensive review and critical analysis of advancements in the CO_(2)-assisted oxidative dehydrogenation of light alkanes(C2-C4)on metal-based catalysts developed in recent years.Moreover,it offers a comparative summary of the structural properties,catalytic activities,and reaction mechanisms over various active sites,providing valuable insights for the future design of dehydrogenation catalysts.展开更多
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...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.展开更多
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...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.展开更多
文摘The efficient hydrogenolysis of esters to alkanes is the key protocol for producing advanced biofuels from renewable plant oils or fats.Due to the low reactivity of the carbonyl group in esters,a high reaction temperature(>250℃)is the prerequisite to ensure high conversion of esters.Here,we report a highly dispersed MoO_(x)-Ru/C bimetallic catalyst for the efficient hydrogenolysis of esters to alkanes under 150°C.The optimal catalyst exhibits>99%conversion of methyl stearate and 99%selectivity to diesel-range alkanes,reaching a high rate of up to 2.0 mmol gcat^(–1)h^(–1),5 times higher than that of Ru/C catalyst(MoO_(x)/C is inert).Integrated experimental and theoretical investigations attribute the high performance to the abundant MoO_(x)-Ru interfacial sites on the catalyst surface,which offers high activity for the C–O cleavage of esters.Furthermore,the dispersed MoO_(x)species significantly weaken the hydrocracking activity of the metallic Ru for C–C bonds,thus yielding alkane products without carbon loss.This study provides a facile and novel strategy for the design of high-performance heterogeneous catalysts for the hydrodeoxygenation of biomass-derived esters to alkane products.
文摘Aromatization of light alkanes is a value-added process in both petrochemical and coal chemical industries.Here,single[Ga(OH)]^(2+)ion-exchanged mesoporous hollow-structured ZSM-5(Ga-MH-ZSM-5)material was prepared,and it shows unprecedented catalytic performance in light alkane aromatization,considering activity,product selectivity and catalytic stability.The average aromatics yields in ethane aromatization at 600℃and WHSV of 0.8 h^(-1) within 28 h and in propane aromatization at 580℃and WHSV of 1.1 h^(-1) within 20 h reach~18.4%and~70.8%with benzene,toluene and xylenes(BTX)accounting for~96%and~88%of aromatics,respectively.Ga-MH-ZSM-5-0.41 gave a TON for formation of aromatics(TON_(aromatics))from propane as high as 57479,whereas the reported catalysts maximally show a TON_(aromatics) of 5514.This also holds true for ethane aromatization;the TON_(aromatics) obtained on Ga-MH-ZSM-5-0.41 was³3845 in contrast to£392 on reported non-noble metal catalysts.The catalytic activity of Ga-MH-ZSM-5 highly depends on Ga species structures.[Ga(OH)]^(2+)ions are predominant species at Ga loading≤0.3 wt%,while more[Ga(OH)_(2)]^(+)and GaO_(x) oligomers are formed with increasing Ga content.Upon reduction with H_(2),[Ga(OH)]^(2+)and[Ga(OH)_(2)]^(+)are transformed into[GaH]^(2+)and[GaH_(2)]^(+)species,which show a propane dehydrogenation rate of 300 and 15 times of that of Brønsted acid sites respectively.The light alkanes are mainly dehydrogenated into light olefins on[GaH]^(2+)species,and then,oligomerized and cyclized into(alkyl)cycloalkanes on H^(+)sites,which is followed by possible ring expansion on H^(+)and sequential dehydrogenations into aromatics primarily on[GaH]^(2+).
基金National Natural Science Foundation of China(22278084)State Key Laboratory of Heavy Oil Processing(SKLHOP202402003)for financing this research.
文摘To achieve palm oil conversion along with a high yield of long‐chain alkane,a series of NiFe layered double oxide catalysts were prepared and employed in the deoxygenation of palm oil.The layered structure of these catalysts was confirmed by XRD and SEM analyses,and Ni and Fe species existed primarily in the forms of Ni^(2+)and Fe^(3+),respectively.It was found that Ni/Fe molar ratio influenced the H_(2)reducibility and surface properties of NiFe catalysts.Specifically,Ni_(2)Fe‐LDO and Ni_(3)Fe‐LDO exhibited higher reducibility under H_(2)atmosphere.Moreover,the Ni_(2)Fe‐LDO catalyst contained a higher concentration of surface oxygen species(Osurf).Deoxygenation results demonstrated that the Ni_(2)Fe‐LDO catalyst achieved superior palm oil conversion,higher liquid product yield and enhanced selectivity toward C_(15)–C_(18)hydrocarbons compared to other catalysts.This improved performance was attributed to its higher hydrogen dissociation activity and enhanced adsorption capacity for palm oil molecules.Furthermore,reaction condition studies revealed that palm oil was completely converted,yielding 86.8%liquid product with 81.8%selectivity of C_(15)–C_(18)hydrocarbons at 350℃under 7 MPa H_(2)pressure.This finding provides an insight into the development of efficient catalysts for the deoxygenation of fatty compounds to biofuels.
基金supported by the National Natural Science Foundation of China(21676300)~~
文摘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.
基金financially supported by the National Natural Science Foundation of China(No.41772124)National Science and Technology Major Project(No.2016ZX05007001-002).
文摘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.
文摘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.
基金supported by the National Natural Science Foundation of China (21322606,21436005,21576095)the State Key Laboratory of Pulp and Paper Engineering (2015TS03)+2 种基金the Doctoral Fund of Ministry of Education of China (20120172110012)Fundamental Research Funds for the Central Universities (2015ZP002,2015PT004)Guangdong Natural Science Foundation (2013B090500027)
文摘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.
基金financial support from National Natural Science Foundation of China(21776074,21576081,and21861132019)
文摘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.
文摘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.
基金supported by State Key Program of the National Natural Science Foundation of China(21733002)the National Natural Science Foundation of China(U1462120,21403027)Cheung Kong Scholars Programme of China(T2015036)~~
文摘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.
基金funded by the National Key Research and Development Program (2017YFB0306505)
文摘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.
基金This work was supported by the National Natural Science Foundation of China （No.21072053 and No.20772028） and the Scientific Research Fund of Hunan Provincial Education Department （No.10K025 and No.09C386）.
文摘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.
基金Supported by the National Natural Science Foundation of China(41472120)General Project of National Natural Science Foundation of China(42272188)+1 种基金Special Fund of PetroChina and New Energy Branch(2023YQX10101)Petrochemical Joint Fund of Fund Committee(U20B6001)。
文摘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.
文摘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.
文摘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.
基金support from Russian Foundation for Basic Research(Grant No 03-03-32105)is gratefully acknowledged.
文摘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.
基金the National Natural Science Foundation of China(Nos.20862009 and 20962010)the National Natural Science Foundation of Jiangxi Province(No.2008GQH0026)the Science Foundation of Education Department of Jiangxi Province(No.GJJ10386) for their financial support
文摘An efficient synthetic method for bis（indol-3-yl）alkane derivatives has been developed.In the presence of 5 mol%of pyridinium tribromide（PTB）,the condensation of indoles and aldehydes proceeded smoothly under mild conditions,giving rise to the corresponding bis（indol-3-yl）alkanes in good to excellent yields.
文摘Light olefins are important platform feedstocks in the petrochemical industry,and the ongoing global economic development has driven sustained growth in demand for these compounds.The dehydrogenation of alkanes,derived from shale gas,serves as an alternative olefins production route.Concurrently,the target of realizing carbon neutrality promotes the comprehensive utilization of greenhouse gas.The integrated process of light alkanes dehydrogenation and carbon dioxide reduction(CO_(2)-ODH)can produce light olefins and realize resource utilization of CO_(2),which has gained wide popularity.With the introduction of CO_(2),coke deposition and metal reduction encountered in alkanes dehydrogenation reactions can be effectively suppressed.CO_(2)-assisted alkanes dehydrogenation can also reduce the risk of potential explosion hazard associated with O_(2)-oxidative dehydrogenation reactions.Recent investigations into various metal-based catalysts including mono-and bi-metallic alloys and oxides have displayed promising performances due to their unique properties.This paper provides the comprehensive review and critical analysis of advancements in the CO_(2)-assisted oxidative dehydrogenation of light alkanes(C2-C4)on metal-based catalysts developed in recent years.Moreover,it offers a comparative summary of the structural properties,catalytic activities,and reaction mechanisms over various active sites,providing valuable insights for the future design of dehydrogenation catalysts.
文摘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.
基金supported by the China Postdoctoral Science Foundation (20070420393)China Postdoctoral Special Science Foundation (20081095)PetroChina Science and Technology Project (07-01C-01-07)
文摘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.
