Petroleum leakage is a major groundwater contamination source,with chemical composition of water soluble fractions(WSFs)from diverse oil sources significantly impacting groundwater quality and source identification.Th...Petroleum leakage is a major groundwater contamination source,with chemical composition of water soluble fractions(WSFs)from diverse oil sources significantly impacting groundwater quality and source identification.The aim of this study was to assess impact of 15 diverse oils on groundwater quality and environmental forensics based on oil-water equilibrium experiments.Our results indicate that contamination of groundwater by gasoline and naphtha is primarily attributed to volatile hydrocarbons,while pollution from diesel,kerosene,and crude oil is predominantly from non-hydrocarbons.Rapid determination of the extent of non-hydrocarbon pollution in WSFs was achieved through a new quantitative index.Gasoline and naphtha exhibited the highest groundwater contamination potential while kerosene and light crude oils were also likely to cause groundwater contamina-tion.Although volatile hydrocarbons in the WSFs of diesel and jet fuel do not easily exceed current regulatory standards,unregulated non-hydrocarbons may pose a more severe contamination risk to groundwater.Notably,the presence of significant benzene and toluene,hydrogenation and alkylation products(e.g.,C4-C5 alkylben-zenes,alkylindenes,alkyltetralins,and dihydro-indenes),cycloalkanes in WSFs can effectively be utilized for preliminary source identification of light distillates,middle distillates,and crude oils,respectively.展开更多
China possesses abundant heavy oil resources,yet faces challenges such as high viscosity,underdeveloped production technologies,and elevated development cost.Although the in-situ catalytic viscosity-reduction technolo...China possesses abundant heavy oil resources,yet faces challenges such as high viscosity,underdeveloped production technologies,and elevated development cost.Although the in-situ catalytic viscosity-reduction technology can address certain technical,environmental,and cost problems during the extraction process,the catalysts often suffer from poor stability and low catalytic efficiency.In this study,a green and simple room-temperature stirring method was employed to synthesize a class of highly efficient and stable 2D MOF catalysts,which possess the capability to conduct in-situ catalytic pyrolysis of heavy oil and reduce the viscosity.Under the condition of 160℃,a catalyst concentration of 0.5 wt%,and a hydrogen donor(tetralin)concentration of 2 wt%,the viscosity-reduction rate of Fe-MOF is as high as 89.09%,and it can decrease the asphaltene content by 8.42%.In addition,through the structural identification and analysis of crude oil asphaltenes,the causes for the high viscosity of heavy oil are explained at the molecular level.Through the analysis of catalytic products and molecular dynamics simulation,the catalytic mechanism is studied.It is discovered that Fe-MOF can interact with heavy oil macromolecules via coordination and pore-channel effects,facilitating their cracking and dispersal.Furthermore,synergistic interactions between Fe-MOF and the hydrogen donor facilitates hydrogenation reactions and enhances the viscosity-reducing effect.This study provides a novel strategy for boosting heavy oil recovery and underscores the potential of 2D MOFs in catalytic pyrolysis applications.展开更多
The dissolved hydrogen, rather than gaseous hydrogen, plays a crucial role in the hydrogenation process. A thorough understanding of hydrogen dissolution is essential for optimizing the hydrogenation process. In this ...The dissolved hydrogen, rather than gaseous hydrogen, plays a crucial role in the hydrogenation process. A thorough understanding of hydrogen dissolution is essential for optimizing the hydrogenation process. In this paper, the dynamic pressure step method was modified to reduce the temperature difference between the hydrogen and solution, from which the hydrogen solubility and volumetric liquid-side mass transfer coefficient (k_(L)a) of the vacuum residue were obtained. It was discovered that temperature was the most critical factor in hydrogen dissolution, simultaneously enhancing both the hydrogen solubility and k_(L)a. Pressure played a significant role in promoting hydrogen solubility, but had a relatively small impact on kLa. Stirring speed, although it enhanced k_(L)a, did not affect hydrogen solubility. By normalizing the dissolution parameter, the results showed that the gas-liquid mass transfer rate decreased continuously during hydrogen dissolution and that the SD-tD curves after normalization were almost the same in all experimental conditions.展开更多
The influences of reaction temperature,duration,pressure,and catalyst concentration on the molecular transformation of residual slurry phase hydrocracking process were investigated.The molecular composition of the het...The influences of reaction temperature,duration,pressure,and catalyst concentration on the molecular transformation of residual slurry phase hydrocracking process were investigated.The molecular composition of the heteroatom compounds in the residue feedstock and its upgrading products were characterized using high-resolution Orbitrap mass spectrometry coupled with multiple ionization methods.The simultaneous promotion of cracking and hydrogenation reactions was observed with increasing of the reaction temperature and time.Specifically,there was a significant increase in the cracking degree of alkyl side chain,while the removal of low-condensation sulfur compounds such as sulfides and benzothiophenes was enhanced.In particular,the cracking reactions were more significantly facilitated by high temperatures,while an appropriately extended reaction time can result in the complete elimination of the aforementioned sulfur compounds with a lower degree of condensation.Under conditions of low hydrogen pressure and catalyst concentration,the products still exhibit a high relative abundance of easily convertible compounds such as sulfoxides,indicating a significant deficiency in the effectiveness of hydrogenation.The hydrogen pressure exhibits an optimal value,beyond which further increments have no effect on the composition and performance of the liquid product but can increase the yield of the liquid product.At significantly high catalyst concentration,the effect of desulfurization and deoxidation slightly diminishes,while the aromatic saturation of highly condensed compounds was notably enhanced.This hydrogenation saturation effect cannot be attained through manipulation of other operational parameters,thereby potentially benefiting subsequent product processing and utilization.This present study demonstrates a profound comprehension of the molecular-level residue slurry phase hydrocracking process,offering not only specific guide for process design and optimization but also valuable fundamental data for constructing reaction models at the molecular level.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
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
Steam flooding is a widely used technique to enhance oil recovery of heavy oil.Thermal viscosity reduction and distillation effect are considered as two main displacement mechanisms in steam flooding process.However,t...Steam flooding is a widely used technique to enhance oil recovery of heavy oil.Thermal viscosity reduction and distillation effect are considered as two main displacement mechanisms in steam flooding process.However,the molecular composition understanding and contribution for oil production are still unclear.In this study,the composition analysis of the heavy oil was investigated in the core scale steam flooding process with the temperature from 120 to 280℃.The crude oil,produced oils and residual oils were characterized comprehensively by gas chromatography and high-resolution mass spectrometry.It is found that steam flooding preferentially extracts aromatics and remains more resins in the residual oil.Viscosity reduction is the dominant mechanism when steam is injected at a low temperature.Large molecular heteroatoms with high carbon number and high double bond equivalent(DBE)are eluted into the produced oil,while compounds with low carbon number and low DBE are remained in the residual oil.As the steam temperature rises,the increased distillation effect results in the extraction of light hydrocarbons from the residual oil to the produced oil.More small heteroatoms with low carbon number and low DBE enter into the produced oil,especially in the none water cut stage.The compositional difference of produced oils is characterized in DBE versus carbon number distribution of the N and O containing compound classes.This work uses a variety of composition analysis methods to clarify the steam flooding mechanism and provides a novel understanding of steam flooding mechanisms with various temperatures and production stages from the molecular perspective.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
Upgrading of abundant cellulosic biomass to isosorbide can reduce the dependence on limited fossil resources and provide a sustainable way to produce isosorbide,utilized for polymers,medicine and health care product s...Upgrading of abundant cellulosic biomass to isosorbide can reduce the dependence on limited fossil resources and provide a sustainable way to produce isosorbide,utilized for polymers,medicine and health care product synth-esis.This review comprehensively examines the key steps and catalytic systems involved in the conversion of cel-lulose to isosorbide.Initially,the reaction pathway from cellulose to isosorbide is elucidated,emphasizing three critical steps:cellulose hydrolysis,glucose hydrogenation,and the two-step dehydration of sorbitol to produce isosorbide.Additionally,the activation energy and acidic sites during cellulose hydrolysis,the impact of metal particle size and catalyst support on hydrogenation,and the effects of catalyst acidity,pore structure,and reaction conditions on sorbitol dehydration have been thoroughly examined.Finally,the progress made in cellulose con-version to isosorbide is summarized,current challenges are highlighted,and future development trends are pro-jected in this review.展开更多
Coking at the fractionating tower bottom and the decant oil circulation system disrupts the heat balance,leading to unplanned shutdown and destroying the long period stable operation of the Fluid Catalytic Cracking Un...Coking at the fractionating tower bottom and the decant oil circulation system disrupts the heat balance,leading to unplanned shutdown and destroying the long period stable operation of the Fluid Catalytic Cracking Unit(FCCU).The FCCU operates through interconnected subsystems,generating high-dimensional,nonlinear,and non-stationary data characterized by spatiotemporally correlated.The decant oil solid content is the crucial indicator for monitoring catalyst loss from the reactor-regenerator system and coking risk tendency at the fractionating tower bottom that relies on sampling and laboratory testing,which is lagging responsiveness and labor-intensive.Developing the online decant oil solid content soft sensor using industrial data to support operators in conducting predictive maintenance is essential.Therefore,this paper proposes a hybrid deep learning framework for soft sensor development that combines spatiotemporal pattern extraction with interpretability,enabling accurate risk identification in dynamic operational conditions.This framework employs a Filter-Wrapper method for dimensionality reduction,followed by a 2D Convolutional Neural Network(2DCNN)for extracting spatial patterns,and a Bidirectional Gated Recurrent Unit(BiGRU)for capturing long-term temporal dependencies,with an Attention Mechanism(AM)to highlight critical features adaptively.The integration of SHapley Additive exPlanations(SHAP),Complementary Ensemble Empirical Mode Decomposition with Adaptive Noise(CEEMDAN),2DCNN,and expert knowledge precisely quantifies feature contributions and decomposes signals,significantly enhancing the practicality of risk identification.Applied to a China refinery with processing capacity of 2.80×10^(6) t/a,the soft sensor achieved the R^(2) value of 0.93 and five-level risk identification accuracy of 96.42%.These results demonstrate the framework's accuracy,robustness,and suitability for complex industrial scenarios,advancing risk visualization and management.展开更多
Metal-support interactions and hydrogen spillover effects in heterogeneous catalysts play a crucial role in aromatic hydrogenation reactions;however,these effects are limited by the metal dispersion on the catalyst an...Metal-support interactions and hydrogen spillover effects in heterogeneous catalysts play a crucial role in aromatic hydrogenation reactions;however,these effects are limited by the metal dispersion on the catalyst and the number of acceptable H*receptors.This study prepares highly dispersed Ni nanoparticles(NPs)catalysts on a Beta substrate via precursor structure topology transformation.In contrast to traditional support materials,the coordination and electronic structure changes between the Ni NPs and the support were achieved,further optimizing the active interface sites and enhancing hydrogen activation and hydrogenation performance.Additionally,the-OH groups at the strong acid sites in zeolite effectively intensified the hydrogen spillover effect as receptors for H^(*)migration and anchoring,accelerating the hydrogenation rate of aromatic rings.Under solvent-free conditions,this catalyst was used for the hydrogenation reaction of aromatic-rich oils,directly producing a C_(8)-C_(14)branched cycloalkanes mixture with an aromatic conversion rate of>99%.The cycloalkanes mixture produced by this method features high density(0.92 g/mL)and a low freezing point(<-60℃),making it suitable for use as high-density aviation fuel or as an additive to enhance the volumetric heat value of conventional aviation fuels in practical applications.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
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
基金supported by the National Science Foundation of China(Nos.42177042,and 42477051)the National Key R&D Program of China(No.2023YFC3708700)the Science Foundation of China University of Petroleum-Beijing(No.2462022QNXZ006).
文摘Petroleum leakage is a major groundwater contamination source,with chemical composition of water soluble fractions(WSFs)from diverse oil sources significantly impacting groundwater quality and source identification.The aim of this study was to assess impact of 15 diverse oils on groundwater quality and environmental forensics based on oil-water equilibrium experiments.Our results indicate that contamination of groundwater by gasoline and naphtha is primarily attributed to volatile hydrocarbons,while pollution from diesel,kerosene,and crude oil is predominantly from non-hydrocarbons.Rapid determination of the extent of non-hydrocarbon pollution in WSFs was achieved through a new quantitative index.Gasoline and naphtha exhibited the highest groundwater contamination potential while kerosene and light crude oils were also likely to cause groundwater contamina-tion.Although volatile hydrocarbons in the WSFs of diesel and jet fuel do not easily exceed current regulatory standards,unregulated non-hydrocarbons may pose a more severe contamination risk to groundwater.Notably,the presence of significant benzene and toluene,hydrogenation and alkylation products(e.g.,C4-C5 alkylben-zenes,alkylindenes,alkyltetralins,and dihydro-indenes),cycloalkanes in WSFs can effectively be utilized for preliminary source identification of light distillates,middle distillates,and crude oils,respectively.
基金supported by the National Natural Science Foundation of China(52174047)Sinopec Project(No.P23138).
文摘China possesses abundant heavy oil resources,yet faces challenges such as high viscosity,underdeveloped production technologies,and elevated development cost.Although the in-situ catalytic viscosity-reduction technology can address certain technical,environmental,and cost problems during the extraction process,the catalysts often suffer from poor stability and low catalytic efficiency.In this study,a green and simple room-temperature stirring method was employed to synthesize a class of highly efficient and stable 2D MOF catalysts,which possess the capability to conduct in-situ catalytic pyrolysis of heavy oil and reduce the viscosity.Under the condition of 160℃,a catalyst concentration of 0.5 wt%,and a hydrogen donor(tetralin)concentration of 2 wt%,the viscosity-reduction rate of Fe-MOF is as high as 89.09%,and it can decrease the asphaltene content by 8.42%.In addition,through the structural identification and analysis of crude oil asphaltenes,the causes for the high viscosity of heavy oil are explained at the molecular level.Through the analysis of catalytic products and molecular dynamics simulation,the catalytic mechanism is studied.It is discovered that Fe-MOF can interact with heavy oil macromolecules via coordination and pore-channel effects,facilitating their cracking and dispersal.Furthermore,synergistic interactions between Fe-MOF and the hydrogen donor facilitates hydrogenation reactions and enhances the viscosity-reducing effect.This study provides a novel strategy for boosting heavy oil recovery and underscores the potential of 2D MOFs in catalytic pyrolysis applications.
基金supported by the National Key R&D Program of China(No.2022YFB4101300)National Natural Science Foundation of China(NSFC)(No.22278430 and 21878329)Project of R&D Department of CNPC(2020B-2011 and 21-CB-05-05).
文摘The dissolved hydrogen, rather than gaseous hydrogen, plays a crucial role in the hydrogenation process. A thorough understanding of hydrogen dissolution is essential for optimizing the hydrogenation process. In this paper, the dynamic pressure step method was modified to reduce the temperature difference between the hydrogen and solution, from which the hydrogen solubility and volumetric liquid-side mass transfer coefficient (k_(L)a) of the vacuum residue were obtained. It was discovered that temperature was the most critical factor in hydrogen dissolution, simultaneously enhancing both the hydrogen solubility and k_(L)a. Pressure played a significant role in promoting hydrogen solubility, but had a relatively small impact on kLa. Stirring speed, although it enhanced k_(L)a, did not affect hydrogen solubility. By normalizing the dissolution parameter, the results showed that the gas-liquid mass transfer rate decreased continuously during hydrogen dissolution and that the SD-tD curves after normalization were almost the same in all experimental conditions.
基金supported by the National Key R&D Program of China(2021YFA1501200)the National Natural Science Foundation of China(NSFC U23B20169 and 22021004)the Project of R&D Department of CNPC(2020B-2011)。
文摘The influences of reaction temperature,duration,pressure,and catalyst concentration on the molecular transformation of residual slurry phase hydrocracking process were investigated.The molecular composition of the heteroatom compounds in the residue feedstock and its upgrading products were characterized using high-resolution Orbitrap mass spectrometry coupled with multiple ionization methods.The simultaneous promotion of cracking and hydrogenation reactions was observed with increasing of the reaction temperature and time.Specifically,there was a significant increase in the cracking degree of alkyl side chain,while the removal of low-condensation sulfur compounds such as sulfides and benzothiophenes was enhanced.In particular,the cracking reactions were more significantly facilitated by high temperatures,while an appropriately extended reaction time can result in the complete elimination of the aforementioned sulfur compounds with a lower degree of condensation.Under conditions of low hydrogen pressure and catalyst concentration,the products still exhibit a high relative abundance of easily convertible compounds such as sulfoxides,indicating a significant deficiency in the effectiveness of hydrogenation.The hydrogen pressure exhibits an optimal value,beyond which further increments have no effect on the composition and performance of the liquid product but can increase the yield of the liquid product.At significantly high catalyst concentration,the effect of desulfurization and deoxidation slightly diminishes,while the aromatic saturation of highly condensed compounds was notably enhanced.This hydrogenation saturation effect cannot be attained through manipulation of other operational parameters,thereby potentially benefiting subsequent product processing and utilization.This present study demonstrates a profound comprehension of the molecular-level residue slurry phase hydrocracking process,offering not only specific guide for process design and optimization but also valuable fundamental data for constructing reaction models at the molecular level.
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.
文摘Steam flooding is a widely used technique to enhance oil recovery of heavy oil.Thermal viscosity reduction and distillation effect are considered as two main displacement mechanisms in steam flooding process.However,the molecular composition understanding and contribution for oil production are still unclear.In this study,the composition analysis of the heavy oil was investigated in the core scale steam flooding process with the temperature from 120 to 280℃.The crude oil,produced oils and residual oils were characterized comprehensively by gas chromatography and high-resolution mass spectrometry.It is found that steam flooding preferentially extracts aromatics and remains more resins in the residual oil.Viscosity reduction is the dominant mechanism when steam is injected at a low temperature.Large molecular heteroatoms with high carbon number and high double bond equivalent(DBE)are eluted into the produced oil,while compounds with low carbon number and low DBE are remained in the residual oil.As the steam temperature rises,the increased distillation effect results in the extraction of light hydrocarbons from the residual oil to the produced oil.More small heteroatoms with low carbon number and low DBE enter into the produced oil,especially in the none water cut stage.The compositional difference of produced oils is characterized in DBE versus carbon number distribution of the N and O containing compound classes.This work uses a variety of composition analysis methods to clarify the steam flooding mechanism and provides a novel understanding of steam flooding mechanisms with various temperatures and production stages from the molecular perspective.
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.
文摘Upgrading of abundant cellulosic biomass to isosorbide can reduce the dependence on limited fossil resources and provide a sustainable way to produce isosorbide,utilized for polymers,medicine and health care product synth-esis.This review comprehensively examines the key steps and catalytic systems involved in the conversion of cel-lulose to isosorbide.Initially,the reaction pathway from cellulose to isosorbide is elucidated,emphasizing three critical steps:cellulose hydrolysis,glucose hydrogenation,and the two-step dehydration of sorbitol to produce isosorbide.Additionally,the activation energy and acidic sites during cellulose hydrolysis,the impact of metal particle size and catalyst support on hydrogenation,and the effects of catalyst acidity,pore structure,and reaction conditions on sorbitol dehydration have been thoroughly examined.Finally,the progress made in cellulose con-version to isosorbide is summarized,current challenges are highlighted,and future development trends are pro-jected in this review.
基金supported by the Innovative Research Group Project of the National Natural Science Foundation of China(22021004)Sinopec Major Science and Technology Projects(321123-1)。
文摘Coking at the fractionating tower bottom and the decant oil circulation system disrupts the heat balance,leading to unplanned shutdown and destroying the long period stable operation of the Fluid Catalytic Cracking Unit(FCCU).The FCCU operates through interconnected subsystems,generating high-dimensional,nonlinear,and non-stationary data characterized by spatiotemporally correlated.The decant oil solid content is the crucial indicator for monitoring catalyst loss from the reactor-regenerator system and coking risk tendency at the fractionating tower bottom that relies on sampling and laboratory testing,which is lagging responsiveness and labor-intensive.Developing the online decant oil solid content soft sensor using industrial data to support operators in conducting predictive maintenance is essential.Therefore,this paper proposes a hybrid deep learning framework for soft sensor development that combines spatiotemporal pattern extraction with interpretability,enabling accurate risk identification in dynamic operational conditions.This framework employs a Filter-Wrapper method for dimensionality reduction,followed by a 2D Convolutional Neural Network(2DCNN)for extracting spatial patterns,and a Bidirectional Gated Recurrent Unit(BiGRU)for capturing long-term temporal dependencies,with an Attention Mechanism(AM)to highlight critical features adaptively.The integration of SHapley Additive exPlanations(SHAP),Complementary Ensemble Empirical Mode Decomposition with Adaptive Noise(CEEMDAN),2DCNN,and expert knowledge precisely quantifies feature contributions and decomposes signals,significantly enhancing the practicality of risk identification.Applied to a China refinery with processing capacity of 2.80×10^(6) t/a,the soft sensor achieved the R^(2) value of 0.93 and five-level risk identification accuracy of 96.42%.These results demonstrate the framework's accuracy,robustness,and suitability for complex industrial scenarios,advancing risk visualization and management.
基金financially supported by the National Natural Science Foundation of China(Grant 22278439,21776313)the Shandong Province Higher Education Youth Innovation Technology Support Program(Grant 2022KJ074)。
文摘Metal-support interactions and hydrogen spillover effects in heterogeneous catalysts play a crucial role in aromatic hydrogenation reactions;however,these effects are limited by the metal dispersion on the catalyst and the number of acceptable H*receptors.This study prepares highly dispersed Ni nanoparticles(NPs)catalysts on a Beta substrate via precursor structure topology transformation.In contrast to traditional support materials,the coordination and electronic structure changes between the Ni NPs and the support were achieved,further optimizing the active interface sites and enhancing hydrogen activation and hydrogenation performance.Additionally,the-OH groups at the strong acid sites in zeolite effectively intensified the hydrogen spillover effect as receptors for H^(*)migration and anchoring,accelerating the hydrogenation rate of aromatic rings.Under solvent-free conditions,this catalyst was used for the hydrogenation reaction of aromatic-rich oils,directly producing a C_(8)-C_(14)branched cycloalkanes mixture with an aromatic conversion rate of>99%.The cycloalkanes mixture produced by this method features high density(0.92 g/mL)and a low freezing point(<-60℃),making it suitable for use as high-density aviation fuel or as an additive to enhance the volumetric heat value of conventional aviation fuels in practical applications.
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.
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.
