Heavy oil is an important resource in current petroleum exploitation, and the chemical composition information of heavy oil is crucial for revealing its viscosity-inducing mechanism and solving practical exploitation ...Heavy oil is an important resource in current petroleum exploitation, and the chemical composition information of heavy oil is crucial for revealing its viscosity-inducing mechanism and solving practical exploitation issues. In this study, the techniques of high-temperature gas chromatography and high-resolution mass spectrometry equipped with an electrospray ionization source were applied to reveal the chemical composition of typical heavy oils from western, central, and eastern China. The results indicate that these heavy oils display significant variations in their bulk properties, with initial boiling points all above 200℃. Utilizing pre-treatment and ESI high-resolution mass spectrometry, an analysis of the molecular composition of saturated hydrocarbons, aromatic hydrocarbons, acidic oxygen compounds, sulfur compounds, basic nitrogen compounds, and neutral nitrogen compounds within the heavy oil was conducted. Ultimately, a semi-quantitative analysis of the molecular composition of the heavy oil was achieved by integrating the elemental content. The semi-quantitative analysis results of Shengli-J8 heavy oil and a conventional Shengli crude oil show that Shengli-J8 heavy oil lacks alkanes and low molecular weight aromatic hydrocarbons, which contributes to its high viscosity. Additionally,characteristic molecular sets for different heavy oils were identified based on the semi-quantitative analysis of molecular composition. The semi-quantitative analysis of molecular composition in heavy oils may provide valuable reference data for establishing theoretical models on the viscosity-inducing mechanism in heavy oils and designing viscosity-reducing agents for heavy oil exploitation.展开更多
As by-products of petroleum refining,heavy oils are characterized by a high carbon content,low cost and great variability,making them competitive precursors for the anodes of potassium ion batteries(PIBs).However,the ...As by-products of petroleum refining,heavy oils are characterized by a high carbon content,low cost and great variability,making them competitive precursors for the anodes of potassium ion batteries(PIBs).However,the relationship between heavy oil composition and potassium storage performance remains unclear.Using heavy oils containing distinct chemical groups as the carbon source,namely fluid catalytic cracking slurry(FCCS),petroleum asphalt(PA)and deoiled asphalt(DOA),three carbon nanosheets(CNS)were prepared through a molten salt method,and used as the anodes for PIBs.The composition of the heavy oil determines the lamellar thicknesses,sp^(3)-C/sp^(2)-C ratio and defect concentration,thereby affecting the potassium storage performance.The high content of aromatic hydrocarbons and moderate amount of heavy component moieties in FCCS produce carbon nanosheets(CNS-FCCS)that have a smaller layer thickness,larger interlayer spacing(0.372 nm),and increased number of folds than in CNS derived from the other three precursors.These features give it faster charge/ion transfer,more potassium storage sites and better reaction kinetics.CNS-FCCS has a remarkable K^(+)storage capacity(248.7 mAh g^(-1) after 100 cycles at 0.1 A g^(-1)),long cycle lifespan(190.8 mAh g^(-1) after 800 cycles at 1.0 A g^(-1))and excellent rate capability,ranking it among the best materials for this application.This work sheds light on the influence of heavy oil composition on carbon structure and electrochemical performance,and provides guidance for the design and development of advanced heavy oil-derived carbon electrodes for PIBs.展开更多
Acquiring accurate molecular-level information about petroleum is crucial for refining and chemical enterprises to implement the“selection of the optimal processing route”strategy.With the development of data predic...Acquiring accurate molecular-level information about petroleum is crucial for refining and chemical enterprises to implement the“selection of the optimal processing route”strategy.With the development of data prediction systems represented by machine learning,it has become possible for real-time prediction systems of petroleum fraction molecular information to replace analyses such as gas chromatography and mass spectrometry.However,the biggest difficulty lies in acquiring the data required for training the neural network.To address these issues,this work proposes an innovative method that utilizes the Aspen HYSYS and full two-dimensional gas chromatography-time-of-flight mass spectrometry to establish a comprehensive training database.Subsequently,a deep neural network prediction model is developed for heavy distillate oil to predict its composition in terms of molecular structure.After training,the model accurately predicts the molecular composition of catalytically cracked raw oil in a refinery.The validation and test sets exhibit R2 values of 0.99769 and 0.99807,respectively,and the average relative error of molecular composition prediction for raw materials of the catalytic cracking unit is less than 7%.Finally,the SHAP(SHapley Additive ExPlanation)interpretation method is used to disclose the relationship among different variables by performing global and local weight comparisons and correlation analyses.展开更多
The primary impediment to the recovery of heavy oil lies in its high viscosity, which necessitates a deeper understanding of the molecular mechanisms governing its dynamic behavior for enhanced oil recovery. However, ...The primary impediment to the recovery of heavy oil lies in its high viscosity, which necessitates a deeper understanding of the molecular mechanisms governing its dynamic behavior for enhanced oil recovery. However, there remains a dearth of understanding regarding the complex molecular composition inherent to heavy oil. In this study, we employed high-resolution mass spectrometry in conjunction with various chemical derivatization and ionization methods to obtain semi-quantitative results of molecular group compositions of 35 heavy oils. The gradient boosting(GB) model has been further used to acquire the feature importance rank(FIR). A feature is an independently observable property of the observed object. Feature importance can measure the contribution of each input feature to the model prediction result, indicate the degree of correlation between the feature and the target,unveil which features are indicative of certain predictions. We have developed a framework for utilizing physical insights into the impact of molecular group compositions on viscosity. The results of machine learning(ML) conducted by GB show that the viscosity of heavy oils is primarily influenced by light components, specifically small molecular hydrocarbons with low condensation degrees, as well as petroleum acids composed of acidic oxygen groups and neutral nitrogen groups. Additionally, large molecular aromatic hydrocarbons and sulfoxides also play significant roles in determine the viscosity.展开更多
It is useful for practical operation to study the rules of production of propylene by the catalytic conversion of heavy oil in FCC （fluid catalytic cracking）. The effects of temperature and C/O ratio （catalyst to o...It is useful for practical operation to study the rules of production of propylene by the catalytic conversion of heavy oil in FCC （fluid catalytic cracking）. The effects of temperature and C/O ratio （catalyst to oil weight ratio） on the distribution of the product and the yield of propylene were investigated on a micro reactor unit with two model catalysts, namely ZSM-5/Al2O3 and USY/Al2O3, and Fushun vacuum gas oil （VGO） was used as the feedstock. The conversion of heavy oil over ZSM-5 catalyst can be comparable to that of USY catalyst at high temperature and high C/O ratio. The rate of conversion of heavy oil using the ZSM-5 equilibrium catalyst is lower compared with the USY equilibrium catalyst under the general FCC conditions and this can be attributed to the poor steam ability of the ZSM-5 equilibrium catalyst. The difference in pore topologies of USY and ZSM-5 is the reason why the principal products for the above two catalysts is different, namely gasoline and liquid petroleum gas （LPG）, repspectively. So the LPG selectivity, especially the propylene selectivity, may decline if USY is added into the FCC catalyst for maximizing the production of propylene. Increasing the C/O ratio is the most economical method for the increase of LPG yield than the increase of the temperature of the two model catalysts, because the loss of light oil is less in the former case. There is an inverse correlation between HTC （hydrogen transfer coefficient） and the yield of propylene, and restricting the hydrogen transfer reaction is the more important measure in increasing the yield of propylene of the ZSM-5 catalyst. The ethylene yield of ZSM-5/A1203 is higher, but the gaseous side products with low value are not enhanced when ZSM-5 catalyst is used. Moreover, for LPG and the end products, dry gas and coke, their ranges of reaction conditions to which their yields are dependent are different, and that of end products is more severe than that of LPG. So it is clear that maximizing LPG and propylene and restricting dry gas and coke can be both achieved via increasing the severity of reaction conditions among the range of reaction conditions which LPG yield is sensitive to.展开更多
This paper investigated the secondary cracking of gasoline and diesel from the catalytic pyrolysis of Daqing atmospheric residue on catalyst CEP-1 in a fluidized bed reactor.The results show that the secondary crackin...This paper investigated the secondary cracking of gasoline and diesel from the catalytic pyrolysis of Daqing atmospheric residue on catalyst CEP-1 in a fluidized bed reactor.The results show that the secondary cracking reactivity of gasoline and diesel is poor,and the yield of total light olefins is only about 10%(by mass).As reaction temperature increases,ethylene yield increases,butylene yield decreases,and propylene yield shows a maximum.The optimal reaction temperature is about 670℃for the production of light olefins.With the enhance- ment of catalyst-to-oil mass ratio and steam-to-oil mass ratio,the yields of light olefins increase to some extent. About 6.30%of the mass of total aromatic rings is converted by secondary cracking,indicating that aromatic hy- drocarbons are not easy to undergo ring-opening reactions under the present experimental conditions.展开更多
In order to develop the conversion of heavy oil with a high yield of propylene in the catalytic cracking process, ZSM-5 zeolite was modified by tungsten and phosphorus, which was proved to be an effective method. Char...In order to develop the conversion of heavy oil with a high yield of propylene in the catalytic cracking process, ZSM-5 zeolite was modified by tungsten and phosphorus, which was proved to be an effective method. Characterization results show that the improvement of catalytic performance could be correlated to the interaction of phosphorus and tungsten species on ZSM-5. P inhibited the aggregation of tungsten species on ZSM-5 and was conductive to convert the tungsten species with octahedral coordination into tetrahedral coordination. And this ultimately led to that more acid sites were reserved after hydrothermal treatment in the tungsten and phosphorus co-modified ZSM-5 catalyst. Phosphorus species played an important role to restrain the dehydrogenation activity of tungsten. In addition, a model reflecting the interaction between tungsten species and ZSM-5 framework was proposed.展开更多
A few-layered hexagonal boron nitride nanosheets stabilized platinum nanoparticles(Pt/h-BNNS)is engineered for oxidation-promoted adsorptive desulfurization(OPADS)of fuel oil.It was found that the few-layered structur...A few-layered hexagonal boron nitride nanosheets stabilized platinum nanoparticles(Pt/h-BNNS)is engineered for oxidation-promoted adsorptive desulfurization(OPADS)of fuel oil.It was found that the few-layered structure and the defective sites of h-BNNS not only are beneficial to the stabilization of Pt NPs but also favor the adsorption of aromatic sulfides.By employing Pt/h-BNNS with a Pt loading amount of 1.19 wt%as the active adsorbent and air as an oxidant,a 98.0%sulfur removal over dibenzothiophene(DBT)is achieved along with a total conversion of the DBT to the corresponding sulfones(DBTO_(2)).Detailed experiments show that the excellent desulfurization activity originates from the few-layered structure of h-BNNS and the high catalytic activity of Pt NPs.In addition,the OPADS system with Pt/h-BNNS as the active adsorbent shows remarkable stability in desulfurization performance with the existence of different interferents such as olefin,and aromatic hydrocarbons.Besides,the Pt/h-BNNS can be recycled 12 times without a significant decrease in desulfurization performance.Also,a process flow diagram is proposed for deep desulfurization of fuel oil and recovery of high value-added products,which would promote the industrial application of such OPADS strategy.展开更多
Light alkanes non-oxidative dehydrogenation is an attractive non-oil route for olefins production.The alkane dehydrogenation reaction is limited by thermodynamic equilibrium,and the C-H bond cleavage is commonly consi...Light alkanes non-oxidative dehydrogenation is an attractive non-oil route for olefins production.The alkane dehydrogenation reaction is limited by thermodynamic equilibrium,and the C-H bond cleavage is commonly considered as the rate-determined step.The valence state of metal sites in catalysts will influence the stabilization of the vital intermediate(i.e.,C_(x)H_(y)...M^(δ+)...H)during the C-H bond cleavage process,which in turn affects the catalytic reactivity.Herein,we explicitly investigated the effect of different valence states of framework-Fe in silicate-1 zeolite on ethane dehydrogenation reaction through the combination of experimental and theoretical study.Fe(Ⅱ)-S-1 and Fe(Ⅲ)-S-1 catalysts are successfully synthesized by ligand-assisted in situ crystallization method,In-situ C_(2)H_6-FTIR shows the higher coverage of hydrocarbon intermediates on Fe(Ⅱ)-S-1,Under the same evaluation co nditio n,Fe(Ⅱ)-S-1 exhibits a higher space time yield of ethylene.Density functional theory(DFT)results reveal that the more coordinate-unsaturated and electron-enriched Fe(Ⅱ)sites boost the first C-H bond activation by slight deformation and efficient electron donation with C_(2)H_(5)^(*)species.Remarkably,the second C-H bond cleavage on Fe(Ⅱ)-S-1 undergoes a spin-crossing process from quintet state to triplet state,which involves a two-electro n-two-orbital interaction,further promoting the formation of ethylene.Microkinetic analysis is consistent with the experimental and DFT results.This work could provide methodology for elucidating the effect of metal valence states on catalytic performance as well as offer guidance for designing more efficient Fe-zeolite catalysts.展开更多
The chemical structure of heavy oil fractions obtained by liquid-solid adsorption chromatography was character-ized by 1 H nuclear magnetic resonance and X-ray diffraction.The molecular weight and molecular formula of...The chemical structure of heavy oil fractions obtained by liquid-solid adsorption chromatography was character-ized by 1 H nuclear magnetic resonance and X-ray diffraction.The molecular weight and molecular formula of asphaltene molecules were estimated by combining 1 H nuclear magnetic resonance and X-ray diffraction analyses,and were also ob-tained from vapor pressure osmometry and elemental analysis.Heteroatoms,such as S,N,and O atoms,were considered in the construction of average molecular structure of heavy oils.Two important structural parameters were proposed,including the number of alkyl chain substituents to aromatic rings and the number of total rings with heteroatoms.Ultimately,the av-erage molecular structures of polycyclic aromatics,heavy resins and asphaltene molecules were constructed.The number of α-,β-,γ-,and aromatic hydrogen atoms of the constructed average molecular structures fits well with the number of hydro-gen atoms derived from the experimental spectral data.展开更多
Coprocessing of bitumen-derived feeds and biomass through a fluid catalytic cracking(FCC) route has the potential to assist in the reduction of fuel and petroleum product carbon footprints while meeting government reg...Coprocessing of bitumen-derived feeds and biomass through a fluid catalytic cracking(FCC) route has the potential to assist in the reduction of fuel and petroleum product carbon footprints while meeting government regulatory requirements on renewable transportation fuels. This approach is desirable because green house gas(GHG) emissions for producing renewable biofuels are significantly lower than those for fossil fuels, and coprocessing can be executed using existing refining infrastructure to save capital cost. The present study investigates the specific FCC performances of pure heavy gas oil(HGO) derived from oil sands synthetic crude, and a mixture of 15 v% canola oil in HGO using a commercial equilibrium catalyst under typical FCC conditions. Cracking experiments were performed using a bench-scale Advanced Cracking Evaluation(ACE) unit at fixed weight hourly space velocity(WHSV) of 8 h^(-1), 490–530℃, and catalyst/oil ratios of 4–12 g/g. This work focuses on some cracking phenomena resulting from the presence of oxygen in the blendda lower heat requirement for cracking due to the exothermic water formation, which also entails lower hydrogen yield at a given severity. The distribution of feed oxygen in gaseous and liquid products, the mitigation in GHG emissions, and the technological and economical advantages of the coprocessing option are also discussed.展开更多
Heavy oil millisecond gas-phase in-line catalytic dehydrogenation over bifunctional catalysts was adopted to produce low-carbon olefins.In this study,the effect of the uncatalyzed reaction composition and distribution...Heavy oil millisecond gas-phase in-line catalytic dehydrogenation over bifunctional catalysts was adopted to produce low-carbon olefins.In this study,the effect of the uncatalyzed reaction composition and distribution of atmosphere residue(AR)pyrolysis vapor at 650℃ was investigated for the first time.In the pyrolysis vapor,the yield of low-carbon olefins was only 15.2%.The yield of 1-olefin and n-alkanes,which are the primary products of rapid heavy oil pyrolysis,reached approximately 54.0%.To achieve further catalytic dehydrogenation,AR pyrolysis volatiles were catalyzed over single calcium aluminate(C_(12)A_(7)),ZSM-5,and C_(12)A_(7)-ZSM-5(CZ)catalysts at 650℃,which possess different pore structures,and acid-base properties.The ZSM-5 catalyst obtained the highest low-carbon olefin yield after catalytic dehydrogenation of pyrolysis volatiles.Finally,the C_(12)A_(7) and CZ stepwise coupling bifunctional catalysts increased the catalytic activity,and thus increased the higher low-carbon olefin yield but reduced the yields of alkanes and aromatics fraction.Notably,the yields of propylene and butane were important sources of the low-carbon olefins.Thus,heavy oil millisecond gas-phase in-line catalytic dehydrogenation could achieve the maximum conversion of these residues to produce low-carbon olefins.展开更多
Most heavy crude oils underwent biodegradation and generated a significant amount of naphthenic acids. Naphthenic acids are polar compounds with the carboxylic group and are considered as a major factor affecting the ...Most heavy crude oils underwent biodegradation and generated a significant amount of naphthenic acids. Naphthenic acids are polar compounds with the carboxylic group and are considered as a major factor affecting the oil viscosity. However, the relationship between the molecular composition of naphthenic acids and oil viscosity is not well understood. This study examined a “clean” heavy oil with low contents of heteroatoms but had a high content of naphthenic acids. Naphthenic acids were fractionated by distillation and caustic extraction. The molecular composition was characterized by high-resolution Orbitrap mass spectrometry. It was found that the 2- and 3-ring naphthenic monoacids with 15–35 carbon atoms are dominant components of the acid fractions;the caustic extraction is capable of isolating naphthenic acids with less than 35 carbons, which is equivalent to the upper limit of the distillable components, but not those in the residue fraction;the total acid number of the heavy distillates is higher than that of the residue fraction;the viscosity of the distillation fraction increases exponentially with an increased boiling point of the distillates. Blending experiments indicates that there is a strong correlation between the oil viscosity and acids content, although the acid content is only a few percent of the total oil.展开更多
Toluene insoluble matter (TIM) in coker heavy gas oil (CHGO) from oil sands bitumen is harmful to the downstream hydrotreating, and it may be difficult to be removed by conventional filtration. In order to determine i...Toluene insoluble matter (TIM) in coker heavy gas oil (CHGO) from oil sands bitumen is harmful to the downstream hydrotreating, and it may be difficult to be removed by conventional filtration. In order to determine its origin, the TIM must first be separated from CHGO for characterization. Two techniques are described to accomplish this goal. In the ultra-centrifugation approach used in this work, CHGO is blended with a miscible liquid and centrifuged under 366000 G (gravity) force. Through this procedure toluene and hexane diluents yielded TIM contents of 24μg·g-1 and 88μg·g-1 respectively. In an alternative simplified procedure, the initial ultra-centrifugation step is omitted. Several different solvents are evaluated for use as diluents but, in each case, toluene is still used in the subsequent washing steps. TIM contents determined by this method range from 23 to about 200μg·g-1. The amount of TIM separated by means of this method depends primarily on the initial diluent used. Other conditions, such as diluent-oil ratio, water-oil ratio, mixing time, temperature and water pH value, are also studied.展开更多
This study set out to gain a deeper understanding of a fluid catalytic cracking(FCC)coprocessing approach using canola oil mixed with bitumen-derived heavy gas oil(HGO),for the production of partially-renewable gasoli...This study set out to gain a deeper understanding of a fluid catalytic cracking(FCC)coprocessing approach using canola oil mixed with bitumen-derived heavy gas oil(HGO),for the production of partially-renewable gasoline,with respect to its composition and quality.The FCC coprocessing approach may provide an alternative solution to reducing the carbon footprint and to meet government regulatory demands for renewable transportation fuels.In this study,a mixture of 15 v%canola oil in HGO was catalytically cracked with a commercial equilibrium catalyst under typical FCC conditions.Cracking experiments were performed using a bench-scale Advanced Cracking Evaluation(ACE)unit at a fixed weight hourly space velocity of 8 h^(à1),490–530C,and catalyst/oil ratios of 4–12 g/g.The total liquid product samples were injected via an automatic sampler and a prefractionator(to removet254C)into a gas chromatographic system containing a series of columns,traps,and valves designed to separate each of the hydrocarbon types.The analyzer gives detailed hydrocarbon types of à200C gasoline,classified into paraffins,iso-paraffins,olefins,naphthenes,and aromatics by carbon number up to C_(11)(C_(10)for aromatics).For a feed cracked at a given temperature,the gasoline aromatics show the highest selectivity in terms of weight percent conversion,followed by saturated iso-paraffins,saturated naphthenes,unsaturated iso-paraffins,unsaturated naphthenes,unsaturated normal paraffins,and saturated normal paraffins.As conversion increases,both aromatics and saturated iso-paraffins increase monotonically at the expense of other components.Hydrocarbon type analysis and octane numbers with variation in feed type,process severity(temperature and catalyst/oil ratio),and conversion are also presented and discussed.展开更多
An interfacially active cobalt complex,cobalt dodecylbenzenesulfonate,was synthesized.Elemental analysis,atomic absorption spectroscopy,Fourier transform infrared spectroscopy（FT-IR）,thermogravimetric analysis,and s...An interfacially active cobalt complex,cobalt dodecylbenzenesulfonate,was synthesized.Elemental analysis,atomic absorption spectroscopy,Fourier transform infrared spectroscopy（FT-IR）,thermogravimetric analysis,and surface/interfacial tension determination were performed to investigate the properties of the catalyst.Results showed that the synthesized catalyst showed active interfacial behavior,decreasing the surface tension and interfacial tension between heavy oil and liquid phase to below 30 and 1.5 mN/m,respectively.The catalyst was not thermally degraded at a temperature of 400 ℃,indicating its high thermal stability.Catalytic performance of the catalyst was evaluated by carrying out aquathermolysis.The viscosity determination showed that the viscosity of the heavy oil decreased by 38%.The average molecular weight,group compositions,and average molecular structure of various samples were analyzed using elemental analysis,FT-IR,electrospray ionization Fourier transform ion cyclotron resonance（ESI FT-ICR MS）,and ～1H nuclear magnetic resonance.Results indicated that the catalyst could attack the sulfur- and O_2-type heteroatomic compounds in asphaltene and resin,especially the compounds with aromatic structure,leading to a decrease in the molecular weight and then the reduction in the viscosity of heavy oil.Therefore,the synthesized catalyst might find an application in catalytic aquathermolysis of heavy oil,especially for the high-aromaticity heavy oil with high oxygen content.展开更多
There is a great interest in developing cost-efficient nutrients to stimulate microorganisms in indigenous microbial enhanced oil recovery（IMEOR） processes.In the present study,the potential of rice bran as a carbon...There is a great interest in developing cost-efficient nutrients to stimulate microorganisms in indigenous microbial enhanced oil recovery（IMEOR） processes.In the present study,the potential of rice bran as a carbon source for promoting IMEOR was investigated on a laboratory scale.The co-applications of rice bran,K2HPO4 and urea under optimized bio-stimulation conditions significantly increased the production of gases,acids and emulsifiers.The structure and diversity of microbial community greatly changed during the IMEOR process,in which Clostridium sp.,Acidobacteria sp.,Bacillus sp.,and Pseudomonas sp.were dominant.Pressurization,acidification and emulsification due to microbial activities and interactions markedly improved the IMEOR processes.This study indicated that rice bran is a potential carbon source for IMEOR.展开更多
Layer-structured Ruddlesden–Popper(RP)perovskites(RPPs)with decent stability have captured the imagination of the photovoltaic research community and bring hope for boosting the development of perovskite solar cell(P...Layer-structured Ruddlesden–Popper(RP)perovskites(RPPs)with decent stability have captured the imagination of the photovoltaic research community and bring hope for boosting the development of perovskite solar cell(PSC)technology.However,two-dimensional(2D)or quasi-2D RP PSCs are encountered with some challenges of the large exciton binding energy,blocked charge transport and poor film quality,which restrict their photovoltaic performance.Fortunately,these issues can be readily resolved by rationally designing spacer cations of RPPs.This review mainly focuses on how to design the molecular structures of organic spacers and aims to endow RPPs with outstanding photovoltaic applications.We firstly elucidated the important roles of organic spacers in impacting crystallization kinetics,charge transporting ability and stability of RPPs.Then we brought three aspects to attention for designing organic spacers.Finally,we presented the specific molecular structure design strategies for organic spacers of RPPs aiming to improve photovoltaic performance of RP PSCs.These proposed strategies in this review will provide new avenues to develop novel organic spacers for RPPs and advance the development of RPP photovoltaic technology for future applications.展开更多
The ever-increasing integration of electronic devices has inevit-ably caused electromagnetic interference and heat accumulation problems,and dual-function materials with both a high thermal conductivity and high elect...The ever-increasing integration of electronic devices has inevit-ably caused electromagnetic interference and heat accumulation problems,and dual-function materials with both a high thermal conductivity and high electromagnetic wave absorption(EWA)are regarded as an effective strategy for solving these problems.Carbon materials are widely used as thermal and EWA fillers due to their excellent conductivity and outstanding thermal conduction properties,and have become a research hotspot in the field of high thermal conductivity,microwave absorbing materials in recent years.The status of current research progress on carbon-based high thermal-conduction microwave absorption materials,including carbon fibers,carbon nanotubes,graphene and amorphous carbon,is re-viewed,and the influence of the structure of the materials on their absorption and thermal conductivity properties,such as core-shell structure,three-dimensional network structure,and heteroatom doping,is also elaborated.Feasible solutions for the cur-rent problems with these materials are proposed,with the aim of providing valuable guidance for the future design of carbon-based high thermal conduction microwave absorbing materials.展开更多
The nitrogen-containing compounds in Changqing crude oil, its atmospheric residue(AR), and vacuum reside(VR) were characterized by negative and positive ion electrospray ionization(ESI) Fourier transform ion cyclotron...The nitrogen-containing compounds in Changqing crude oil, its atmospheric residue(AR), and vacuum reside(VR) were characterized by negative and positive ion electrospray ionization(ESI) Fourier transform ion cyclotron resonance mass spectrometry(FT-ICR MS). The heteroatom compounds(N_1, N_2, N_1O_1, O_1, and O_2 class species) could be identified by the negative ESI analysis, while the positive mode could only detect the N_1, N_2, and N_1O_1 class species. Among them, the N_1 class species were found to be predominant in crude oil, as confirmed by either negative or positive ESI analyses,which were similar in composition to AR and VR. These compounds with higher abundance were characterized by double bond equivalent(DBE) values and carbon numbers. The composition of these compounds in crude oil and its AR as well as VR was correlated with their different boiling range, DBE values and carbon numbers. The negative ESI analysis showed that the abundant N_1 class species in crude oil and AR were centered at a DBE value of 12, and these species were likely benzocarbazoles, while the N_1 class species with the DBE value ranging from 13 to 16 having more complicated molecular structures were dominant in VR. And the positive ESI analysis gave the information of the abundant N_1 class species in crude oil, AR, and VR having the DBE values in the range of 10, 9―11, and 10―16, respectively, which were likely the compounds with the core of quinoline and benzoquinoline. The analysis confirmed that the distillation process in refinery preferentially removed the low DBE value and low molecular N-class species and brought them into the light and medium distillates, while those N-class species having a high molecular condensation in the molecules with large carbon number remained in the residual oil and could continually affect the downstream oil refining process.展开更多
基金supported by the National Key R&D Program of China (2018YFA0702400)the Science Foundation of China University of Petroleum, Beijing (2462023QNXZ017)。
文摘Heavy oil is an important resource in current petroleum exploitation, and the chemical composition information of heavy oil is crucial for revealing its viscosity-inducing mechanism and solving practical exploitation issues. In this study, the techniques of high-temperature gas chromatography and high-resolution mass spectrometry equipped with an electrospray ionization source were applied to reveal the chemical composition of typical heavy oils from western, central, and eastern China. The results indicate that these heavy oils display significant variations in their bulk properties, with initial boiling points all above 200℃. Utilizing pre-treatment and ESI high-resolution mass spectrometry, an analysis of the molecular composition of saturated hydrocarbons, aromatic hydrocarbons, acidic oxygen compounds, sulfur compounds, basic nitrogen compounds, and neutral nitrogen compounds within the heavy oil was conducted. Ultimately, a semi-quantitative analysis of the molecular composition of the heavy oil was achieved by integrating the elemental content. The semi-quantitative analysis results of Shengli-J8 heavy oil and a conventional Shengli crude oil show that Shengli-J8 heavy oil lacks alkanes and low molecular weight aromatic hydrocarbons, which contributes to its high viscosity. Additionally,characteristic molecular sets for different heavy oils were identified based on the semi-quantitative analysis of molecular composition. The semi-quantitative analysis of molecular composition in heavy oils may provide valuable reference data for establishing theoretical models on the viscosity-inducing mechanism in heavy oils and designing viscosity-reducing agents for heavy oil exploitation.
文摘As by-products of petroleum refining,heavy oils are characterized by a high carbon content,low cost and great variability,making them competitive precursors for the anodes of potassium ion batteries(PIBs).However,the relationship between heavy oil composition and potassium storage performance remains unclear.Using heavy oils containing distinct chemical groups as the carbon source,namely fluid catalytic cracking slurry(FCCS),petroleum asphalt(PA)and deoiled asphalt(DOA),three carbon nanosheets(CNS)were prepared through a molten salt method,and used as the anodes for PIBs.The composition of the heavy oil determines the lamellar thicknesses,sp^(3)-C/sp^(2)-C ratio and defect concentration,thereby affecting the potassium storage performance.The high content of aromatic hydrocarbons and moderate amount of heavy component moieties in FCCS produce carbon nanosheets(CNS-FCCS)that have a smaller layer thickness,larger interlayer spacing(0.372 nm),and increased number of folds than in CNS derived from the other three precursors.These features give it faster charge/ion transfer,more potassium storage sites and better reaction kinetics.CNS-FCCS has a remarkable K^(+)storage capacity(248.7 mAh g^(-1) after 100 cycles at 0.1 A g^(-1)),long cycle lifespan(190.8 mAh g^(-1) after 800 cycles at 1.0 A g^(-1))and excellent rate capability,ranking it among the best materials for this application.This work sheds light on the influence of heavy oil composition on carbon structure and electrochemical performance,and provides guidance for the design and development of advanced heavy oil-derived carbon electrodes for PIBs.
基金the National Natural Science Foundation of China(22108307)the Natural Science Foundation of Shandong Province(ZR2020KB006)the Outstanding Youth Fund of Shandong Provincial Natural Science Foundation(ZR2020YQ17).
文摘Acquiring accurate molecular-level information about petroleum is crucial for refining and chemical enterprises to implement the“selection of the optimal processing route”strategy.With the development of data prediction systems represented by machine learning,it has become possible for real-time prediction systems of petroleum fraction molecular information to replace analyses such as gas chromatography and mass spectrometry.However,the biggest difficulty lies in acquiring the data required for training the neural network.To address these issues,this work proposes an innovative method that utilizes the Aspen HYSYS and full two-dimensional gas chromatography-time-of-flight mass spectrometry to establish a comprehensive training database.Subsequently,a deep neural network prediction model is developed for heavy distillate oil to predict its composition in terms of molecular structure.After training,the model accurately predicts the molecular composition of catalytically cracked raw oil in a refinery.The validation and test sets exhibit R2 values of 0.99769 and 0.99807,respectively,and the average relative error of molecular composition prediction for raw materials of the catalytic cracking unit is less than 7%.Finally,the SHAP(SHapley Additive ExPlanation)interpretation method is used to disclose the relationship among different variables by performing global and local weight comparisons and correlation analyses.
基金supported by the National Key R&D Program of China (2018YFA0702400)。
文摘The primary impediment to the recovery of heavy oil lies in its high viscosity, which necessitates a deeper understanding of the molecular mechanisms governing its dynamic behavior for enhanced oil recovery. However, there remains a dearth of understanding regarding the complex molecular composition inherent to heavy oil. In this study, we employed high-resolution mass spectrometry in conjunction with various chemical derivatization and ionization methods to obtain semi-quantitative results of molecular group compositions of 35 heavy oils. The gradient boosting(GB) model has been further used to acquire the feature importance rank(FIR). A feature is an independently observable property of the observed object. Feature importance can measure the contribution of each input feature to the model prediction result, indicate the degree of correlation between the feature and the target,unveil which features are indicative of certain predictions. We have developed a framework for utilizing physical insights into the impact of molecular group compositions on viscosity. The results of machine learning(ML) conducted by GB show that the viscosity of heavy oils is primarily influenced by light components, specifically small molecular hydrocarbons with low condensation degrees, as well as petroleum acids composed of acidic oxygen groups and neutral nitrogen groups. Additionally, large molecular aromatic hydrocarbons and sulfoxides also play significant roles in determine the viscosity.
文摘It is useful for practical operation to study the rules of production of propylene by the catalytic conversion of heavy oil in FCC （fluid catalytic cracking）. The effects of temperature and C/O ratio （catalyst to oil weight ratio） on the distribution of the product and the yield of propylene were investigated on a micro reactor unit with two model catalysts, namely ZSM-5/Al2O3 and USY/Al2O3, and Fushun vacuum gas oil （VGO） was used as the feedstock. The conversion of heavy oil over ZSM-5 catalyst can be comparable to that of USY catalyst at high temperature and high C/O ratio. The rate of conversion of heavy oil using the ZSM-5 equilibrium catalyst is lower compared with the USY equilibrium catalyst under the general FCC conditions and this can be attributed to the poor steam ability of the ZSM-5 equilibrium catalyst. The difference in pore topologies of USY and ZSM-5 is the reason why the principal products for the above two catalysts is different, namely gasoline and liquid petroleum gas （LPG）, repspectively. So the LPG selectivity, especially the propylene selectivity, may decline if USY is added into the FCC catalyst for maximizing the production of propylene. Increasing the C/O ratio is the most economical method for the increase of LPG yield than the increase of the temperature of the two model catalysts, because the loss of light oil is less in the former case. There is an inverse correlation between HTC （hydrogen transfer coefficient） and the yield of propylene, and restricting the hydrogen transfer reaction is the more important measure in increasing the yield of propylene of the ZSM-5 catalyst. The ethylene yield of ZSM-5/A1203 is higher, but the gaseous side products with low value are not enhanced when ZSM-5 catalyst is used. Moreover, for LPG and the end products, dry gas and coke, their ranges of reaction conditions to which their yields are dependent are different, and that of end products is more severe than that of LPG. So it is clear that maximizing LPG and propylene and restricting dry gas and coke can be both achieved via increasing the severity of reaction conditions among the range of reaction conditions which LPG yield is sensitive to.
基金Supported by the Major Research Plan of Ministry of Education of China(No.307008).
文摘This paper investigated the secondary cracking of gasoline and diesel from the catalytic pyrolysis of Daqing atmospheric residue on catalyst CEP-1 in a fluidized bed reactor.The results show that the secondary cracking reactivity of gasoline and diesel is poor,and the yield of total light olefins is only about 10%(by mass).As reaction temperature increases,ethylene yield increases,butylene yield decreases,and propylene yield shows a maximum.The optimal reaction temperature is about 670℃for the production of light olefins.With the enhance- ment of catalyst-to-oil mass ratio and steam-to-oil mass ratio,the yields of light olefins increase to some extent. About 6.30%of the mass of total aromatic rings is converted by secondary cracking,indicating that aromatic hy- drocarbons are not easy to undergo ring-opening reactions under the present experimental conditions.
文摘In order to develop the conversion of heavy oil with a high yield of propylene in the catalytic cracking process, ZSM-5 zeolite was modified by tungsten and phosphorus, which was proved to be an effective method. Characterization results show that the improvement of catalytic performance could be correlated to the interaction of phosphorus and tungsten species on ZSM-5. P inhibited the aggregation of tungsten species on ZSM-5 and was conductive to convert the tungsten species with octahedral coordination into tetrahedral coordination. And this ultimately led to that more acid sites were reserved after hydrothermal treatment in the tungsten and phosphorus co-modified ZSM-5 catalyst. Phosphorus species played an important role to restrain the dehydrogenation activity of tungsten. In addition, a model reflecting the interaction between tungsten species and ZSM-5 framework was proposed.
基金financial support from the National Natural Science Foundation of China(22178154,22008094,21908082,21878133)Natural Science Foundation of Jiangsu Province(BK20190852,BK20190854)Natural Science Foundation for Jiangsu Colleges and Universities(19KJB530005).
文摘A few-layered hexagonal boron nitride nanosheets stabilized platinum nanoparticles(Pt/h-BNNS)is engineered for oxidation-promoted adsorptive desulfurization(OPADS)of fuel oil.It was found that the few-layered structure and the defective sites of h-BNNS not only are beneficial to the stabilization of Pt NPs but also favor the adsorption of aromatic sulfides.By employing Pt/h-BNNS with a Pt loading amount of 1.19 wt%as the active adsorbent and air as an oxidant,a 98.0%sulfur removal over dibenzothiophene(DBT)is achieved along with a total conversion of the DBT to the corresponding sulfones(DBTO_(2)).Detailed experiments show that the excellent desulfurization activity originates from the few-layered structure of h-BNNS and the high catalytic activity of Pt NPs.In addition,the OPADS system with Pt/h-BNNS as the active adsorbent shows remarkable stability in desulfurization performance with the existence of different interferents such as olefin,and aromatic hydrocarbons.Besides,the Pt/h-BNNS can be recycled 12 times without a significant decrease in desulfurization performance.Also,a process flow diagram is proposed for deep desulfurization of fuel oil and recovery of high value-added products,which would promote the industrial application of such OPADS strategy.
基金the financial support from the National Natural Science Foundation of China (22035009,22178381)the National Key R&D Program of China (2021YFA1501301,2021YFC2901100)。
文摘Light alkanes non-oxidative dehydrogenation is an attractive non-oil route for olefins production.The alkane dehydrogenation reaction is limited by thermodynamic equilibrium,and the C-H bond cleavage is commonly considered as the rate-determined step.The valence state of metal sites in catalysts will influence the stabilization of the vital intermediate(i.e.,C_(x)H_(y)...M^(δ+)...H)during the C-H bond cleavage process,which in turn affects the catalytic reactivity.Herein,we explicitly investigated the effect of different valence states of framework-Fe in silicate-1 zeolite on ethane dehydrogenation reaction through the combination of experimental and theoretical study.Fe(Ⅱ)-S-1 and Fe(Ⅲ)-S-1 catalysts are successfully synthesized by ligand-assisted in situ crystallization method,In-situ C_(2)H_6-FTIR shows the higher coverage of hydrocarbon intermediates on Fe(Ⅱ)-S-1,Under the same evaluation co nditio n,Fe(Ⅱ)-S-1 exhibits a higher space time yield of ethylene.Density functional theory(DFT)results reveal that the more coordinate-unsaturated and electron-enriched Fe(Ⅱ)sites boost the first C-H bond activation by slight deformation and efficient electron donation with C_(2)H_(5)^(*)species.Remarkably,the second C-H bond cleavage on Fe(Ⅱ)-S-1 undergoes a spin-crossing process from quintet state to triplet state,which involves a two-electro n-two-orbital interaction,further promoting the formation of ethylene.Microkinetic analysis is consistent with the experimental and DFT results.This work could provide methodology for elucidating the effect of metal valence states on catalytic performance as well as offer guidance for designing more efficient Fe-zeolite catalysts.
基金the funding of the National Basic Research Program of China (Grant No.2006CB202505)
文摘The chemical structure of heavy oil fractions obtained by liquid-solid adsorption chromatography was character-ized by 1 H nuclear magnetic resonance and X-ray diffraction.The molecular weight and molecular formula of asphaltene molecules were estimated by combining 1 H nuclear magnetic resonance and X-ray diffraction analyses,and were also ob-tained from vapor pressure osmometry and elemental analysis.Heteroatoms,such as S,N,and O atoms,were considered in the construction of average molecular structure of heavy oils.Two important structural parameters were proposed,including the number of alkyl chain substituents to aromatic rings and the number of total rings with heteroatoms.Ultimately,the av-erage molecular structures of polycyclic aromatics,heavy resins and asphaltene molecules were constructed.The number of α-,β-,γ-,and aromatic hydrogen atoms of the constructed average molecular structures fits well with the number of hydro-gen atoms derived from the experimental spectral data.
基金analytical laboratory of CanmetENERGY-Devon for its technical supportSuncor Energy Inc.for supplying the synthetic crude oil.Partial funding for this study was provided by Natural Resources Canada and the Government of Canada's Interdepartmental Program of Energy Research and Development(PERD)
文摘Coprocessing of bitumen-derived feeds and biomass through a fluid catalytic cracking(FCC) route has the potential to assist in the reduction of fuel and petroleum product carbon footprints while meeting government regulatory requirements on renewable transportation fuels. This approach is desirable because green house gas(GHG) emissions for producing renewable biofuels are significantly lower than those for fossil fuels, and coprocessing can be executed using existing refining infrastructure to save capital cost. The present study investigates the specific FCC performances of pure heavy gas oil(HGO) derived from oil sands synthetic crude, and a mixture of 15 v% canola oil in HGO using a commercial equilibrium catalyst under typical FCC conditions. Cracking experiments were performed using a bench-scale Advanced Cracking Evaluation(ACE) unit at fixed weight hourly space velocity(WHSV) of 8 h^(-1), 490–530℃, and catalyst/oil ratios of 4–12 g/g. This work focuses on some cracking phenomena resulting from the presence of oxygen in the blendda lower heat requirement for cracking due to the exothermic water formation, which also entails lower hydrogen yield at a given severity. The distribution of feed oxygen in gaseous and liquid products, the mitigation in GHG emissions, and the technological and economical advantages of the coprocessing option are also discussed.
基金the financial sponsored by the CNPC Innovation Found(No.2022DQ02-0402)the Natural Science Basic Research Program of Shaanxi(No.2024JC-YBMS-085)+2 种基金Shandong Provincial Postdoctoral Science Foundation(No.SDCX-ZG-202303044)the State Key Laboratory of Heavy Oil Processing(No.SKLHOP202201004,No.SKLHOP202403001)the Graduate Student Innovation and Practical Ability Training Program of Xi'an Shiyou University(No.YCS23213078).
文摘Heavy oil millisecond gas-phase in-line catalytic dehydrogenation over bifunctional catalysts was adopted to produce low-carbon olefins.In this study,the effect of the uncatalyzed reaction composition and distribution of atmosphere residue(AR)pyrolysis vapor at 650℃ was investigated for the first time.In the pyrolysis vapor,the yield of low-carbon olefins was only 15.2%.The yield of 1-olefin and n-alkanes,which are the primary products of rapid heavy oil pyrolysis,reached approximately 54.0%.To achieve further catalytic dehydrogenation,AR pyrolysis volatiles were catalyzed over single calcium aluminate(C_(12)A_(7)),ZSM-5,and C_(12)A_(7)-ZSM-5(CZ)catalysts at 650℃,which possess different pore structures,and acid-base properties.The ZSM-5 catalyst obtained the highest low-carbon olefin yield after catalytic dehydrogenation of pyrolysis volatiles.Finally,the C_(12)A_(7) and CZ stepwise coupling bifunctional catalysts increased the catalytic activity,and thus increased the higher low-carbon olefin yield but reduced the yields of alkanes and aromatics fraction.Notably,the yields of propylene and butane were important sources of the low-carbon olefins.Thus,heavy oil millisecond gas-phase in-line catalytic dehydrogenation could achieve the maximum conversion of these residues to produce low-carbon olefins.
基金supported by the National Key R&D Program of China(2018YFA0702400)Science Foundation of China University of Petroleum,Beijing(ZX20210029).
文摘Most heavy crude oils underwent biodegradation and generated a significant amount of naphthenic acids. Naphthenic acids are polar compounds with the carboxylic group and are considered as a major factor affecting the oil viscosity. However, the relationship between the molecular composition of naphthenic acids and oil viscosity is not well understood. This study examined a “clean” heavy oil with low contents of heteroatoms but had a high content of naphthenic acids. Naphthenic acids were fractionated by distillation and caustic extraction. The molecular composition was characterized by high-resolution Orbitrap mass spectrometry. It was found that the 2- and 3-ring naphthenic monoacids with 15–35 carbon atoms are dominant components of the acid fractions;the caustic extraction is capable of isolating naphthenic acids with less than 35 carbons, which is equivalent to the upper limit of the distillable components, but not those in the residue fraction;the total acid number of the heavy distillates is higher than that of the residue fraction;the viscosity of the distillation fraction increases exponentially with an increased boiling point of the distillates. Blending experiments indicates that there is a strong correlation between the oil viscosity and acids content, although the acid content is only a few percent of the total oil.
基金CHGO sample was provided by Synrude Canada Ltd.Plant.
文摘Toluene insoluble matter (TIM) in coker heavy gas oil (CHGO) from oil sands bitumen is harmful to the downstream hydrotreating, and it may be difficult to be removed by conventional filtration. In order to determine its origin, the TIM must first be separated from CHGO for characterization. Two techniques are described to accomplish this goal. In the ultra-centrifugation approach used in this work, CHGO is blended with a miscible liquid and centrifuged under 366000 G (gravity) force. Through this procedure toluene and hexane diluents yielded TIM contents of 24μg·g-1 and 88μg·g-1 respectively. In an alternative simplified procedure, the initial ultra-centrifugation step is omitted. Several different solvents are evaluated for use as diluents but, in each case, toluene is still used in the subsequent washing steps. TIM contents determined by this method range from 23 to about 200μg·g-1. The amount of TIM separated by means of this method depends primarily on the initial diluent used. Other conditions, such as diluent-oil ratio, water-oil ratio, mixing time, temperature and water pH value, are also studied.
基金Natural Resources Canada and government of Canada's interdepartmental Program of Energy Research and Development (PERD)
文摘This study set out to gain a deeper understanding of a fluid catalytic cracking(FCC)coprocessing approach using canola oil mixed with bitumen-derived heavy gas oil(HGO),for the production of partially-renewable gasoline,with respect to its composition and quality.The FCC coprocessing approach may provide an alternative solution to reducing the carbon footprint and to meet government regulatory demands for renewable transportation fuels.In this study,a mixture of 15 v%canola oil in HGO was catalytically cracked with a commercial equilibrium catalyst under typical FCC conditions.Cracking experiments were performed using a bench-scale Advanced Cracking Evaluation(ACE)unit at a fixed weight hourly space velocity of 8 h^(à1),490–530C,and catalyst/oil ratios of 4–12 g/g.The total liquid product samples were injected via an automatic sampler and a prefractionator(to removet254C)into a gas chromatographic system containing a series of columns,traps,and valves designed to separate each of the hydrocarbon types.The analyzer gives detailed hydrocarbon types of à200C gasoline,classified into paraffins,iso-paraffins,olefins,naphthenes,and aromatics by carbon number up to C_(11)(C_(10)for aromatics).For a feed cracked at a given temperature,the gasoline aromatics show the highest selectivity in terms of weight percent conversion,followed by saturated iso-paraffins,saturated naphthenes,unsaturated iso-paraffins,unsaturated naphthenes,unsaturated normal paraffins,and saturated normal paraffins.As conversion increases,both aromatics and saturated iso-paraffins increase monotonically at the expense of other components.Hydrocarbon type analysis and octane numbers with variation in feed type,process severity(temperature and catalyst/oil ratio),and conversion are also presented and discussed.
基金the financial support from the Key Programs of Science and Technology of SINPOEC (Grant No. P11093)
文摘An interfacially active cobalt complex,cobalt dodecylbenzenesulfonate,was synthesized.Elemental analysis,atomic absorption spectroscopy,Fourier transform infrared spectroscopy（FT-IR）,thermogravimetric analysis,and surface/interfacial tension determination were performed to investigate the properties of the catalyst.Results showed that the synthesized catalyst showed active interfacial behavior,decreasing the surface tension and interfacial tension between heavy oil and liquid phase to below 30 and 1.5 mN/m,respectively.The catalyst was not thermally degraded at a temperature of 400 ℃,indicating its high thermal stability.Catalytic performance of the catalyst was evaluated by carrying out aquathermolysis.The viscosity determination showed that the viscosity of the heavy oil decreased by 38%.The average molecular weight,group compositions,and average molecular structure of various samples were analyzed using elemental analysis,FT-IR,electrospray ionization Fourier transform ion cyclotron resonance（ESI FT-ICR MS）,and ～1H nuclear magnetic resonance.Results indicated that the catalyst could attack the sulfur- and O_2-type heteroatomic compounds in asphaltene and resin,especially the compounds with aromatic structure,leading to a decrease in the molecular weight and then the reduction in the viscosity of heavy oil.Therefore,the synthesized catalyst might find an application in catalytic aquathermolysis of heavy oil,especially for the high-aromaticity heavy oil with high oxygen content.
基金supported in part by the National Natural Science Foundation of China (Nos. 51209216 and 21306229)the Korean RDA Grant (No. PJ009472)
文摘There is a great interest in developing cost-efficient nutrients to stimulate microorganisms in indigenous microbial enhanced oil recovery（IMEOR） processes.In the present study,the potential of rice bran as a carbon source for promoting IMEOR was investigated on a laboratory scale.The co-applications of rice bran,K2HPO4 and urea under optimized bio-stimulation conditions significantly increased the production of gases,acids and emulsifiers.The structure and diversity of microbial community greatly changed during the IMEOR process,in which Clostridium sp.,Acidobacteria sp.,Bacillus sp.,and Pseudomonas sp.were dominant.Pressurization,acidification and emulsification due to microbial activities and interactions markedly improved the IMEOR processes.This study indicated that rice bran is a potential carbon source for IMEOR.
基金funding from National Science Foundation of China(52202337 and 22178015)the Young Taishan Scholars Program of Shandong Province(tsqn202211082)+1 种基金Natural Science Foundation of Shandong Province(ZR2023MB051)Independent Innovation Research Project of China University of Petroleum(East China)(22CX06023A).
文摘Layer-structured Ruddlesden–Popper(RP)perovskites(RPPs)with decent stability have captured the imagination of the photovoltaic research community and bring hope for boosting the development of perovskite solar cell(PSC)technology.However,two-dimensional(2D)or quasi-2D RP PSCs are encountered with some challenges of the large exciton binding energy,blocked charge transport and poor film quality,which restrict their photovoltaic performance.Fortunately,these issues can be readily resolved by rationally designing spacer cations of RPPs.This review mainly focuses on how to design the molecular structures of organic spacers and aims to endow RPPs with outstanding photovoltaic applications.We firstly elucidated the important roles of organic spacers in impacting crystallization kinetics,charge transporting ability and stability of RPPs.Then we brought three aspects to attention for designing organic spacers.Finally,we presented the specific molecular structure design strategies for organic spacers of RPPs aiming to improve photovoltaic performance of RP PSCs.These proposed strategies in this review will provide new avenues to develop novel organic spacers for RPPs and advance the development of RPP photovoltaic technology for future applications.
基金financial supports from the National Natural Science Foundation of China(22238012 and 22178384)Science Foundation of China University of Petroleum,Beijing(2462024QNXZ003)。
文摘The ever-increasing integration of electronic devices has inevit-ably caused electromagnetic interference and heat accumulation problems,and dual-function materials with both a high thermal conductivity and high electromagnetic wave absorption(EWA)are regarded as an effective strategy for solving these problems.Carbon materials are widely used as thermal and EWA fillers due to their excellent conductivity and outstanding thermal conduction properties,and have become a research hotspot in the field of high thermal conductivity,microwave absorbing materials in recent years.The status of current research progress on carbon-based high thermal-conduction microwave absorption materials,including carbon fibers,carbon nanotubes,graphene and amorphous carbon,is re-viewed,and the influence of the structure of the materials on their absorption and thermal conductivity properties,such as core-shell structure,three-dimensional network structure,and heteroatom doping,is also elaborated.Feasible solutions for the cur-rent problems with these materials are proposed,with the aim of providing valuable guidance for the future design of carbon-based high thermal conduction microwave absorbing materials.
基金supported by the Young Talent Fund of University Association for Science and Technoloqy in Shaanxi, China (No. 20160222)The PetroChina Innovation Foundation (No. 2016D-5007-0404)the Natural Science Basic Research Plan in Shaanxi Province of China (No. 2017JQ2034)
文摘The nitrogen-containing compounds in Changqing crude oil, its atmospheric residue(AR), and vacuum reside(VR) were characterized by negative and positive ion electrospray ionization(ESI) Fourier transform ion cyclotron resonance mass spectrometry(FT-ICR MS). The heteroatom compounds(N_1, N_2, N_1O_1, O_1, and O_2 class species) could be identified by the negative ESI analysis, while the positive mode could only detect the N_1, N_2, and N_1O_1 class species. Among them, the N_1 class species were found to be predominant in crude oil, as confirmed by either negative or positive ESI analyses,which were similar in composition to AR and VR. These compounds with higher abundance were characterized by double bond equivalent(DBE) values and carbon numbers. The composition of these compounds in crude oil and its AR as well as VR was correlated with their different boiling range, DBE values and carbon numbers. The negative ESI analysis showed that the abundant N_1 class species in crude oil and AR were centered at a DBE value of 12, and these species were likely benzocarbazoles, while the N_1 class species with the DBE value ranging from 13 to 16 having more complicated molecular structures were dominant in VR. And the positive ESI analysis gave the information of the abundant N_1 class species in crude oil, AR, and VR having the DBE values in the range of 10, 9―11, and 10―16, respectively, which were likely the compounds with the core of quinoline and benzoquinoline. The analysis confirmed that the distillation process in refinery preferentially removed the low DBE value and low molecular N-class species and brought them into the light and medium distillates, while those N-class species having a high molecular condensation in the molecules with large carbon number remained in the residual oil and could continually affect the downstream oil refining process.
