We report the results of the experiment on synthesizing ^(287,288)Mc isotopes (Z=115) using the fusionevaporation reaction ^(243)Am(^(48)Ca,4n,3n)^(287,288)Mc at the Spectrometer for Heavy Atoms and Nuclear Structure-...We report the results of the experiment on synthesizing ^(287,288)Mc isotopes (Z=115) using the fusionevaporation reaction ^(243)Am(^(48)Ca,4n,3n)^(287,288)Mc at the Spectrometer for Heavy Atoms and Nuclear Structure-2(SHANS2),a gas-filled recoil separator located at the China Accelerator Facility for Superheavy Elements(CAFE2).In total,20 decay chains are attributed to ^(288)Mc and 1 decay chain is assigned to ^(287)Mc.The measured oa-decay properties of ^(287,288)Mc as well as its descendants are consistent with the known data.No additional decay chains originating from the 2n or 5n reaction channels were detected.The excitation function of the ^(243)Am(^(48)Ca,3n)^(288)Mc reaction was measured at the cross-section level of picobarn,which indicates the promising capability for the study of heavy and superheavy nuclei at the facility.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
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
State-selective single-and double-electron capture processes in collisions of S^(5+)ions with helium at energies ranging from 50.8 keV to 100 keV were investigated using cold target recoil ion momentum spectroscopy(CO...State-selective single-and double-electron capture processes in collisions of S^(5+)ions with helium at energies ranging from 50.8 keV to 100 keV were investigated using cold target recoil ion momentum spectroscopy(COLTRIMS).Q-value spectra and projectile scattering angle distributions were obtained.For single-electron capture,single electron capture into n=3 states of the projectile ion is dominant.As the projectile energy increases,the contribution of single electron capture into n=4 states is observed.Experimental relative cross-sections for single-electron capture into different projectile final states were compared with theoretical predictions based on the molecular orbital close-coupling(MOCC)method.In double-electron capture,two-electron populating into the 3s^(2)3p and 3s3p^(2)states of projectile dominates.The reaction window calculated from the classical molecular Coulombic barrier model can qualitatively explain the experimental results.The scattering angle distribution of the multi-peak structure of the double-electron capture process is observed.The database is openly available in Science Data Bank at https://doi.org/10.57760/sciencedb.j00113.00233.展开更多
We study the fragmentation of NO^(q+)(q=2,3)molecular ions produced by collisions between 96 keV O^(6+)ions and neutral nitric oxide(NO)molecules,using the cold target recoil ion momentum spectrometer(COLTRIMS).The ki...We study the fragmentation of NO^(q+)(q=2,3)molecular ions produced by collisions between 96 keV O^(6+)ions and neutral nitric oxide(NO)molecules,using the cold target recoil ion momentum spectrometer(COLTRIMS).The kinetic energy release(KER)for various dissociation channels is obtained.For the channel NO^(2+)→N^(+)+O^(+),double-electron capture followed by autoionization of the projectile ions is the dominant process,which can be explained by the recapture of loosely bound electrons into highly excited states of the target.For NO3+trication,two dissociation channels,i.e.,(a)N^(+)+O^(2+)and(b)N^(2+)+O^(+),are observed,where channel(b)is the dominant channel.Moreover,for dissociation channels originating from the same parent molecular ion,the dissociation channel with a higher charge for the oxygen ion fragment exhibits a higher most probable KER,which is consistent with studies of CO fragmentation by Rajput et al.Additionally,it is observed that as capture stability increases,the average KER shifts to higher values.展开更多
Aiming at the problems of insufficient activity and selectivity of Cu-based catalysts in CO_(2)hydrogenation to methanol,Al_(2)O_(3),ZrO_(2)and CeO_(2)modified Cu-ZnO catalysts by the co-precipitation method were prep...Aiming at the problems of insufficient activity and selectivity of Cu-based catalysts in CO_(2)hydrogenation to methanol,Al_(2)O_(3),ZrO_(2)and CeO_(2)modified Cu-ZnO catalysts by the co-precipitation method were prepared,and the influence mechanism of additives on the structure-performance relationship of the catalysts was systematically explored.Through a variety of characterization methods such as XRD,N2 physical adsorption-desorption,TEM,H_(2)-TPR,CO_(2)-TPD and XPS,combined with catalytic performance evaluation experiments,the correlation between the microstructure of catalysts and the reaction performance of CO_(2)hydrogenation to methanol was analyzed in depth.The results show that metal additives significantly improve the performance of catalysts.After the introduction of additives,the specific surface area and pore volume of the catalysts increase,the grain size of Cu decreases,and its dispersion improves.The Ce-modified CZC catalyst exhibited the best performance,with the grain size of CuO as small as 11.41 nm,and the surface oxygen vacancy concentration(OⅡ/OⅠ=3.15)was significantly higher than that of other samples.The reaction performance test shows that under the conditions of 2.8 MPa,8000 h−1 and 280℃,the CO_(2)conversion of the CZC catalyst reached 18.83%,the methanol selectivity was 68.40%,and the methanol yield was 12.88%,all of which are superior to other catalysts.Its excellent performance can be attributed to the fact that CeO_(2)enhances the metal-support interaction,increases the surface basicity,promotes the adsorption and activation of CO_(2),and simultaneously inhibits the reverse water-gas shift side reaction.This study clarifies the structure-activity regulation mechanism of additive modification on Cu-ZnO catalysts,providing a theoretical basis and technical reference for the development of efficient catalysts for CO_(2)hydrogenation to methanol.展开更多
Catalytic decomposition of methane,which produces high-purity hydrogen and high-value-added carbon nanomaterials,has shown considerable potential for development and is expected to yield significant economic benefits ...Catalytic decomposition of methane,which produces high-purity hydrogen and high-value-added carbon nanomaterials,has shown considerable potential for development and is expected to yield significant economic benefits in the future.However,designing catalysts that simultaneously exhibit high activity and long-term stability remains a significant challenge.Tuning the catalyst’s structure and electronic properties is an effective strategy for enhancing the reaction performance.In this work,a series of NixZr/ZSM-5 catalysts were prepared using the incipient wetness impregnation method,and the effect of Zr loadings on catalyst properties and performance was systematically investigated.The calcined and reduced catalysts were characterized by low-temperature N_(2)adsorption-desorption,XRD,SEM,H_(2)-TPR and XPS.The results showed that the addition of Zr significantly increased the specific surface area of the catalyst and reduced the metal particle size.Smaller NiO particles were found to enter the pores of the HZSM-5 support,and electronic interactions between NiO and ZrO_(2)markedly enhanced the metal-support interaction.The catalyst exhibited optimal catalytic performance at a Zr loading of 5%,achieving a maximum methane conversion of 68%at 625℃,maintaining activity for 900 min,and delivering a carbon yield of 1927%.Further increasing the Zr loading yielded only limited improvements in catalytic performance.Characterization of the spent catalysts and carbon products via TEM,Raman spectroscopy,and TGA revealed that the introduction of ZrO_(2)reduced metal sintering and promoted a shift in carbon nanofibers growth mode from tip-growth to base-growth.The mechanism of base-growth enabled the catalyst to maintain reaction activity for an extended period.展开更多
Rational design of nanozymes with enhanced catalytic efficiency remains a central challenge in the development of artificial enzymes.Herein,we report the construction of ultrasmall gold nanoclusterbased nanoassemblies...Rational design of nanozymes with enhanced catalytic efficiency remains a central challenge in the development of artificial enzymes.Herein,we report the construction of ultrasmall gold nanoclusterbased nanoassemblies(Dp-Au NCs@Fe^(2+)) through the coordination of Fe^(2+) ions by a dopa-containing peptidomimetic ligand(Dp CDp).This nanoarchitecture simultaneously integrates catalytically active gold cores and redox-active Fe^(2+)centers,bridged by Dp CDp to facilitate directional electron transfer.Comprehensive spectroscopic and kinetic analyses reveal that Dp CDp promotes efficient charge migration from the Au core to surface-bound Fe^(2+),significantly enhancing H_(2)O_(2)-mediated peroxidase-like activity.Compared to bare Dp-Au NCs,Dp-Au NCs@Fe^(2+) display a 4.3-fold improvement in detection sensitivity,a 6.7-fold increase in catalytic efficiency,and markedly stronger hydroxyl radical generation.Mechanistically,this activity stems from a synergistic triad:direct H_(2)O_(2) oxidation at gold surfaces,radical generation at Fe^(2+) sites,and Dp CDp-facilitated electron shuttling.This work presents a robust strategy for nanozyme enhancement via electronic and structural co-engineering,offering valuable insights for the future design of bioinspired catalytic systems.展开更多
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
Developing biomass platform compounds into high value-added chemicals is a key step in renewable resource utilization.Herein,we report porous carbon-supported Ni-ZnO nanoparticles catalyst(Ni-ZnO/AC)synthesized via lo...Developing biomass platform compounds into high value-added chemicals is a key step in renewable resource utilization.Herein,we report porous carbon-supported Ni-ZnO nanoparticles catalyst(Ni-ZnO/AC)synthesized via low-temperature coprecipitation,exhibiting excellent performance for the selective hydrogenation of 5-hydroxymethylfurfural(HMF).A linear correlation is first observed between solvent polarity(E_(T)(30))and product selectivity within both polar aprotic and protic solvent classes,suggesting that solvent properties play a vital role in directing reaction pathways.Among these,1,4-dioxane(aprotic)favors the formation of 2,5-bis(hydroxymethyl)furan(BHMF)with 97.5%selectivity,while isopropanol(iPrOH,protic)promotes 2,5-dimethylfuran production with up to 99.5%selectivity.Mechanistic investigations further reveal that beyond polarity,proton-donating ability is critical in facilitating hydrodeoxygenation.iPrOH enables a hydrogen shuttle mechanism where protons assist in hydroxyl group removal,lowering the activation barrier.In contrast,1,4-dioxane,lacking hydrogen bond donors,stabilizes BHMF and hinders further conversion.Density functional theory calculations confirm a lower activation energy in iPrOH(0.60 eV)compared to 1,4-dioxane(1.07 eV).This work offers mechanistic insights and a practical strategy for solvent-mediated control of product selectivity in biomass hydrogenation,highlighting the decisive role of solvent-catalyst-substrate interactions.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
Rational design of Zn-containing HZSM-5 zeolite(Zn/HZSM-5)with high reactivity and excellent aromatization performance for olefin aromatization is crucially desired.We develop a new and uncomplicated method to synthes...Rational design of Zn-containing HZSM-5 zeolite(Zn/HZSM-5)with high reactivity and excellent aromatization performance for olefin aromatization is crucially desired.We develop a new and uncomplicated method to synthesize Zn/HZSM-5(IMX/Z5)with superior aromatization performance in the paper.Compared to incipient wetness impregnation(IMP/Z5)and mechanical mixing(MIX/Z5),the asprepared IMX/Z5 presents a higher amount of surface ZnOH^(+)species(2.87%)while keeping identical bulk zinc content.As a result,more surface ZnOH^(+)favor both the aromatization of 1-hexene and cyclohexane dehydrogenation.For the two olefin aromatization pathways(hydrogen transfer and dehydrogenation),it is the first time found both the hydrogen transfer ability and the dehydrogenation ability increase linearly with the amount of surface ZnOH^(+)species while keeping identical bulk zinc content.We believe that the linear relationships are essential to design next generation olefin aromatization catalysts.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
This study investigated the susceptibility of X80 pipeline steel to hydrogen embrittlement given different hydrogen pre-charging times and hydrogen charging–releasing–recharging cycles in H2S environment.The fractur...This study investigated the susceptibility of X80 pipeline steel to hydrogen embrittlement given different hydrogen pre-charging times and hydrogen charging–releasing–recharging cycles in H2S environment.The fracture strain of the steel samples decreased with increasing hydrogen pre-charging time;this steel degradation could almost be recovered after diffusible hydrogen was removed when the hydrogen pre-charging time was<8 d.However,unrecoverable degeneration occurred when the hydrogen pre-charging time extended to 16–30 d.Moreover,nanovoid formation meant that the hydrogen damage to the steel under intermittent hydrogen pre-charging–releasing–recharging conditions was more serious than that under continuous hydrogen pre-charging conditions.This study illustrated that the mechanical degradation of steel is inevitable in an H2S environment even if diffusible hydrogen is removed or visible hydrogen-induced cracking is neglected.Furthermore,the steel samples showed premature fractures and exhibited a hydrogen fatigue effect because the repeated entry and release of diffusible hydrogen promoted the formation of vacancies that aggregated into nanovoids.Our results provide valuable information on the mechanical degradation of steel in an H2S environment,regarding the change rules of steel mechanical properties under different hydrogen pre-charging times and hydrogen charging–releasing–recharging cycles.展开更多
A novel porous binder was obtained from acid-treated kaolin. This new binder possessed abundant meso/macropores, good hydrothermal stability and heavy metal resistance. The prepared catalyst using new binder featured ...A novel porous binder was obtained from acid-treated kaolin. This new binder possessed abundant meso/macropores, good hydrothermal stability and heavy metal resistance. The prepared catalyst using new binder featured low attrition index and large pore volume. The catalysts were contaminated with Ni, V, and tested in a fixed-fluidized bed reactor unit. In comparison with the reference sample, the oil conversion achieved by the above-mentioned catalyst increased by 3.50 percentage points, and heavy oil yield decreased by 2.86 percentage points, while the total liquid yield and light oil yield increased by 2.82 percentage points and 0.79 percentage points, respectively. The perfect pore structure, good hydrothermal stability and heavy metal resistant performance of new binder were the possible causes leading to its outstanding performance.展开更多
Local learning based soft sensing methods succeed in coping with time-varying characteristics of processes as well as nonlinearities in industrial plants. In this paper, a local partial least squares based soft sensin...Local learning based soft sensing methods succeed in coping with time-varying characteristics of processes as well as nonlinearities in industrial plants. In this paper, a local partial least squares based soft sensing method for multi-output processes is proposed to accomplish process states division and local model adaptation,which are two key steps in development of local learning based soft sensors. An adaptive way of partitioning process states without redundancy is proposed based on F-test, where unique local time regions are extracted.Subsequently, a novel anti-over-fitting criterion is proposed for online local model adaptation which simultaneously considers the relationship between process variables and the information in labeled and unlabeled samples. Case study is carried out on two chemical processes and simulation results illustrate the superiorities of the proposed method from several aspects.展开更多
The synthesis, characterization and thermal decomposition mechanism of cetyltrimethyl ammonium tetrathiotungstate （CTriMATT） were studied herein. The as-synthesized CTriMATT was characterized by Elemental analysis, ...The synthesis, characterization and thermal decomposition mechanism of cetyltrimethyl ammonium tetrathiotungstate （CTriMATT） were studied herein. The as-synthesized CTriMATT was characterized by Elemental analysis, X-ray diffraction （XRD）, Fourier transform infrared （FT-IR）, Ultraviolet visible （UV-Vis） spectra. The results showed that the as-synthesized CTriMATT had high purity and good crystallinity. The introduction of alkyl groups induced a shift of the stretching vibration band of W-S bond to lower wavenumber, while it had no influence on the position of WS4^2-. Thermogravimetric analysis （TG）, differential thermal analysis （DTA） and in situ XRD characterizations revealed that CTriMATT began to decompose at 423 K in nitrogen and was converted to WS2 eventually. In addition, the decomposition product of CTriMATT at 673 K in nitrogen was characterized by N2 adsorption （BET） and scanning electron microscopy （SEM）. The results demonstrated that WS2 with higher specific surface area, and pore volume could be obtained from the thermal decomposition of CTriMATT in nitrogen.展开更多
基金supported in part by the National Key R&D Program of China (Contract Nos.2023YFA1606500,2024YFE0109800,and 2024YFE0110400)Strategic Priority Research Program of Chinese Academy of Sciences(Grant No.XDB34010000)+5 种基金the Gansu Key Project of Science and Technology (Grant No.23ZDGA014)the Guangdong Major Project of Basic and Applied Basic Research (Grant No.2021B0301030006)the National Natural Science Foundation of China (Grant Nos.12105328,W2412040,12475126,12422507,12035011,12375118,12435008,and W2412043)the Chinese Academy of Sciences Project for Young Scientists in Basic Research(Grant No.YSBR-002)the Youth Innovation Promotion Association of the Chinese Academy of Sciences (Grant Nos.2020409 and 2023439)the Russian Science Foundation (Grant No.25-42-00003)。
文摘We report the results of the experiment on synthesizing ^(287,288)Mc isotopes (Z=115) using the fusionevaporation reaction ^(243)Am(^(48)Ca,4n,3n)^(287,288)Mc at the Spectrometer for Heavy Atoms and Nuclear Structure-2(SHANS2),a gas-filled recoil separator located at the China Accelerator Facility for Superheavy Elements(CAFE2).In total,20 decay chains are attributed to ^(288)Mc and 1 decay chain is assigned to ^(287)Mc.The measured oa-decay properties of ^(287,288)Mc as well as its descendants are consistent with the known data.No additional decay chains originating from the 2n or 5n reaction channels were detected.The excitation function of the ^(243)Am(^(48)Ca,3n)^(288)Mc reaction was measured at the cross-section level of picobarn,which indicates the promising capability for the study of heavy and superheavy nuclei at the facility.
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 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.
基金Project supported by the National Key Research and Development Program of China(Grant No.2022YFA1602500)the National Natural Science Foundation of China(Grant No.11974358)。
文摘State-selective single-and double-electron capture processes in collisions of S^(5+)ions with helium at energies ranging from 50.8 keV to 100 keV were investigated using cold target recoil ion momentum spectroscopy(COLTRIMS).Q-value spectra and projectile scattering angle distributions were obtained.For single-electron capture,single electron capture into n=3 states of the projectile ion is dominant.As the projectile energy increases,the contribution of single electron capture into n=4 states is observed.Experimental relative cross-sections for single-electron capture into different projectile final states were compared with theoretical predictions based on the molecular orbital close-coupling(MOCC)method.In double-electron capture,two-electron populating into the 3s^(2)3p and 3s3p^(2)states of projectile dominates.The reaction window calculated from the classical molecular Coulombic barrier model can qualitatively explain the experimental results.The scattering angle distribution of the multi-peak structure of the double-electron capture process is observed.The database is openly available in Science Data Bank at https://doi.org/10.57760/sciencedb.j00113.00233.
基金supported by the National Key Research and Development Program of China(Grant No.2022YFA1602500)the National Natural Science Foundation of China(Grant Nos.11934004,12064040,and 11974358)Strategic Key Research Program of the Chinese Academy of Sciences(Grant No.XDB34020000).
文摘We study the fragmentation of NO^(q+)(q=2,3)molecular ions produced by collisions between 96 keV O^(6+)ions and neutral nitric oxide(NO)molecules,using the cold target recoil ion momentum spectrometer(COLTRIMS).The kinetic energy release(KER)for various dissociation channels is obtained.For the channel NO^(2+)→N^(+)+O^(+),double-electron capture followed by autoionization of the projectile ions is the dominant process,which can be explained by the recapture of loosely bound electrons into highly excited states of the target.For NO3+trication,two dissociation channels,i.e.,(a)N^(+)+O^(2+)and(b)N^(2+)+O^(+),are observed,where channel(b)is the dominant channel.Moreover,for dissociation channels originating from the same parent molecular ion,the dissociation channel with a higher charge for the oxygen ion fragment exhibits a higher most probable KER,which is consistent with studies of CO fragmentation by Rajput et al.Additionally,it is observed that as capture stability increases,the average KER shifts to higher values.
基金Supported by National Key R&D Program of China(2022YFA1503400)。
文摘Aiming at the problems of insufficient activity and selectivity of Cu-based catalysts in CO_(2)hydrogenation to methanol,Al_(2)O_(3),ZrO_(2)and CeO_(2)modified Cu-ZnO catalysts by the co-precipitation method were prepared,and the influence mechanism of additives on the structure-performance relationship of the catalysts was systematically explored.Through a variety of characterization methods such as XRD,N2 physical adsorption-desorption,TEM,H_(2)-TPR,CO_(2)-TPD and XPS,combined with catalytic performance evaluation experiments,the correlation between the microstructure of catalysts and the reaction performance of CO_(2)hydrogenation to methanol was analyzed in depth.The results show that metal additives significantly improve the performance of catalysts.After the introduction of additives,the specific surface area and pore volume of the catalysts increase,the grain size of Cu decreases,and its dispersion improves.The Ce-modified CZC catalyst exhibited the best performance,with the grain size of CuO as small as 11.41 nm,and the surface oxygen vacancy concentration(OⅡ/OⅠ=3.15)was significantly higher than that of other samples.The reaction performance test shows that under the conditions of 2.8 MPa,8000 h−1 and 280℃,the CO_(2)conversion of the CZC catalyst reached 18.83%,the methanol selectivity was 68.40%,and the methanol yield was 12.88%,all of which are superior to other catalysts.Its excellent performance can be attributed to the fact that CeO_(2)enhances the metal-support interaction,increases the surface basicity,promotes the adsorption and activation of CO_(2),and simultaneously inhibits the reverse water-gas shift side reaction.This study clarifies the structure-activity regulation mechanism of additive modification on Cu-ZnO catalysts,providing a theoretical basis and technical reference for the development of efficient catalysts for CO_(2)hydrogenation to methanol.
基金Supported by Innovative Research Groups of the National Natural Science Foundation of China(22021004)。
文摘Catalytic decomposition of methane,which produces high-purity hydrogen and high-value-added carbon nanomaterials,has shown considerable potential for development and is expected to yield significant economic benefits in the future.However,designing catalysts that simultaneously exhibit high activity and long-term stability remains a significant challenge.Tuning the catalyst’s structure and electronic properties is an effective strategy for enhancing the reaction performance.In this work,a series of NixZr/ZSM-5 catalysts were prepared using the incipient wetness impregnation method,and the effect of Zr loadings on catalyst properties and performance was systematically investigated.The calcined and reduced catalysts were characterized by low-temperature N_(2)adsorption-desorption,XRD,SEM,H_(2)-TPR and XPS.The results showed that the addition of Zr significantly increased the specific surface area of the catalyst and reduced the metal particle size.Smaller NiO particles were found to enter the pores of the HZSM-5 support,and electronic interactions between NiO and ZrO_(2)markedly enhanced the metal-support interaction.The catalyst exhibited optimal catalytic performance at a Zr loading of 5%,achieving a maximum methane conversion of 68%at 625℃,maintaining activity for 900 min,and delivering a carbon yield of 1927%.Further increasing the Zr loading yielded only limited improvements in catalytic performance.Characterization of the spent catalysts and carbon products via TEM,Raman spectroscopy,and TGA revealed that the introduction of ZrO_(2)reduced metal sintering and promoted a shift in carbon nanofibers growth mode from tip-growth to base-growth.The mechanism of base-growth enabled the catalyst to maintain reaction activity for an extended period.
基金supported by the National Natural Science Foundation of China (Nos.22177133,22278438)。
文摘Rational design of nanozymes with enhanced catalytic efficiency remains a central challenge in the development of artificial enzymes.Herein,we report the construction of ultrasmall gold nanoclusterbased nanoassemblies(Dp-Au NCs@Fe^(2+)) through the coordination of Fe^(2+) ions by a dopa-containing peptidomimetic ligand(Dp CDp).This nanoarchitecture simultaneously integrates catalytically active gold cores and redox-active Fe^(2+)centers,bridged by Dp CDp to facilitate directional electron transfer.Comprehensive spectroscopic and kinetic analyses reveal that Dp CDp promotes efficient charge migration from the Au core to surface-bound Fe^(2+),significantly enhancing H_(2)O_(2)-mediated peroxidase-like activity.Compared to bare Dp-Au NCs,Dp-Au NCs@Fe^(2+) display a 4.3-fold improvement in detection sensitivity,a 6.7-fold increase in catalytic efficiency,and markedly stronger hydroxyl radical generation.Mechanistically,this activity stems from a synergistic triad:direct H_(2)O_(2) oxidation at gold surfaces,radical generation at Fe^(2+) sites,and Dp CDp-facilitated electron shuttling.This work presents a robust strategy for nanozyme enhancement via electronic and structural co-engineering,offering valuable insights for the future design of bioinspired catalytic systems.
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the National Nature Science Foundation of China for Excellent Young Scientists Fund(32222058)Fundamental Research Foundation of CAF(CAFYBB2022QB001).
文摘Developing biomass platform compounds into high value-added chemicals is a key step in renewable resource utilization.Herein,we report porous carbon-supported Ni-ZnO nanoparticles catalyst(Ni-ZnO/AC)synthesized via low-temperature coprecipitation,exhibiting excellent performance for the selective hydrogenation of 5-hydroxymethylfurfural(HMF).A linear correlation is first observed between solvent polarity(E_(T)(30))and product selectivity within both polar aprotic and protic solvent classes,suggesting that solvent properties play a vital role in directing reaction pathways.Among these,1,4-dioxane(aprotic)favors the formation of 2,5-bis(hydroxymethyl)furan(BHMF)with 97.5%selectivity,while isopropanol(iPrOH,protic)promotes 2,5-dimethylfuran production with up to 99.5%selectivity.Mechanistic investigations further reveal that beyond polarity,proton-donating ability is critical in facilitating hydrodeoxygenation.iPrOH enables a hydrogen shuttle mechanism where protons assist in hydroxyl group removal,lowering the activation barrier.In contrast,1,4-dioxane,lacking hydrogen bond donors,stabilizes BHMF and hinders further conversion.Density functional theory calculations confirm a lower activation energy in iPrOH(0.60 eV)compared to 1,4-dioxane(1.07 eV).This work offers mechanistic insights and a practical strategy for solvent-mediated control of product selectivity in biomass hydrogenation,highlighting the decisive role of solvent-catalyst-substrate interactions.
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.
基金the support from the National Natural Science Foundation of China(21838011)。
文摘Rational design of Zn-containing HZSM-5 zeolite(Zn/HZSM-5)with high reactivity and excellent aromatization performance for olefin aromatization is crucially desired.We develop a new and uncomplicated method to synthesize Zn/HZSM-5(IMX/Z5)with superior aromatization performance in the paper.Compared to incipient wetness impregnation(IMP/Z5)and mechanical mixing(MIX/Z5),the asprepared IMX/Z5 presents a higher amount of surface ZnOH^(+)species(2.87%)while keeping identical bulk zinc content.As a result,more surface ZnOH^(+)favor both the aromatization of 1-hexene and cyclohexane dehydrogenation.For the two olefin aromatization pathways(hydrogen transfer and dehydrogenation),it is the first time found both the hydrogen transfer ability and the dehydrogenation ability increase linearly with the amount of surface ZnOH^(+)species while keeping identical bulk zinc content.We believe that the linear relationships are essential to design next generation olefin aromatization catalysts.
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financially supported by the National Natural Science Foundation of China (Nos. 51805292, 51671215, and 51425502)the National Postdoctoral Program for Innovative Talents of China (No. BX201700132)
文摘This study investigated the susceptibility of X80 pipeline steel to hydrogen embrittlement given different hydrogen pre-charging times and hydrogen charging–releasing–recharging cycles in H2S environment.The fracture strain of the steel samples decreased with increasing hydrogen pre-charging time;this steel degradation could almost be recovered after diffusible hydrogen was removed when the hydrogen pre-charging time was<8 d.However,unrecoverable degeneration occurred when the hydrogen pre-charging time extended to 16–30 d.Moreover,nanovoid formation meant that the hydrogen damage to the steel under intermittent hydrogen pre-charging–releasing–recharging conditions was more serious than that under continuous hydrogen pre-charging conditions.This study illustrated that the mechanical degradation of steel is inevitable in an H2S environment even if diffusible hydrogen is removed or visible hydrogen-induced cracking is neglected.Furthermore,the steel samples showed premature fractures and exhibited a hydrogen fatigue effect because the repeated entry and release of diffusible hydrogen promoted the formation of vacancies that aggregated into nanovoids.Our results provide valuable information on the mechanical degradation of steel in an H2S environment,regarding the change rules of steel mechanical properties under different hydrogen pre-charging times and hydrogen charging–releasing–recharging cycles.
基金the Department of Science and Technology Management of PetroChina for providing financial support
文摘A novel porous binder was obtained from acid-treated kaolin. This new binder possessed abundant meso/macropores, good hydrothermal stability and heavy metal resistance. The prepared catalyst using new binder featured low attrition index and large pore volume. The catalysts were contaminated with Ni, V, and tested in a fixed-fluidized bed reactor unit. In comparison with the reference sample, the oil conversion achieved by the above-mentioned catalyst increased by 3.50 percentage points, and heavy oil yield decreased by 2.86 percentage points, while the total liquid yield and light oil yield increased by 2.82 percentage points and 0.79 percentage points, respectively. The perfect pore structure, good hydrothermal stability and heavy metal resistant performance of new binder were the possible causes leading to its outstanding performance.
基金Supported by the National Natural Science Foundation of China(61273160)the Fundamental Research Funds for the Central Universities(14CX06067A,13CX05021A)
文摘Local learning based soft sensing methods succeed in coping with time-varying characteristics of processes as well as nonlinearities in industrial plants. In this paper, a local partial least squares based soft sensing method for multi-output processes is proposed to accomplish process states division and local model adaptation,which are two key steps in development of local learning based soft sensors. An adaptive way of partitioning process states without redundancy is proposed based on F-test, where unique local time regions are extracted.Subsequently, a novel anti-over-fitting criterion is proposed for online local model adaptation which simultaneously considers the relationship between process variables and the information in labeled and unlabeled samples. Case study is carried out on two chemical processes and simulation results illustrate the superiorities of the proposed method from several aspects.
基金This work is sponsored by National Key Fundamental Research Development Plan ("973" Plan, No.2004CB217807)the China National Petroleum Corporation (No. B04A50502)
文摘The synthesis, characterization and thermal decomposition mechanism of cetyltrimethyl ammonium tetrathiotungstate （CTriMATT） were studied herein. The as-synthesized CTriMATT was characterized by Elemental analysis, X-ray diffraction （XRD）, Fourier transform infrared （FT-IR）, Ultraviolet visible （UV-Vis） spectra. The results showed that the as-synthesized CTriMATT had high purity and good crystallinity. The introduction of alkyl groups induced a shift of the stretching vibration band of W-S bond to lower wavenumber, while it had no influence on the position of WS4^2-. Thermogravimetric analysis （TG）, differential thermal analysis （DTA） and in situ XRD characterizations revealed that CTriMATT began to decompose at 423 K in nitrogen and was converted to WS2 eventually. In addition, the decomposition product of CTriMATT at 673 K in nitrogen was characterized by N2 adsorption （BET） and scanning electron microscopy （SEM）. The results demonstrated that WS2 with higher specific surface area, and pore volume could be obtained from the thermal decomposition of CTriMATT in nitrogen.
