Propylene is a significant basic material for petrochemicals such as polypropylene,propylene oxide,etc.With abundant propane supply from shale gas,propane dehydrogenation(PDH)becomes extensively attractive as an on-pu...Propylene is a significant basic material for petrochemicals such as polypropylene,propylene oxide,etc.With abundant propane supply from shale gas,propane dehydrogenation(PDH)becomes extensively attractive as an on-purpose propylene production route in recent years.Nitrogen-doped carbon(NC)nanopolyhedra supported cobalt catalysts were synthesized in one-step of ZIF-67 pyrolysis and investigated further in PDH.XPS,TEM and N_(2) adsorption-desorption were used to study the influence of carbonization temperature on as-prepared NC supported cobalt catalysts.The temperature is found to affect the cobalt phase and nitrogen species of the catalysts.And the positive correlation was established between Co0 proportion and space time yield of propylene,indicating that the modulation of carbonization temperature could be important for catalytic performance.展开更多
Carbon catalysts for propane oxidative dehydrogenation(PODH)can potentially replace metal oxide catalysts due to their environmental friendliness(greenness)and excellent catalytic performance.Biomass carbon materials ...Carbon catalysts for propane oxidative dehydrogenation(PODH)can potentially replace metal oxide catalysts due to their environmental friendliness(greenness)and excellent catalytic performance.Biomass carbon materials have the advantages of being abundant in variety,inexpensive,and easily available,but their catalytic selectivity is relatively poor in PODH.Therefore,we report here on a boron-doped sisal fiber carbon catalyst,which showed excellent selectivity of propylene in PODH,excluding the effect of surface-covered B2O3 on the catalytic performance by hot water washing.The carbon material exhibited the best catalytic performance with a load of 2%(mass)and a calcination temperature of 1100℃.At a reaction temperature of 400℃,the conversion rate of propane was 2.0%,and the selectivity toward propylene reached 88.6%.The new chemical bonds formed by boron on the surface of the carbon materials had an important effect on the catalytic performance,as determined by XPS characterization.The BAO groups affected the catalytic activity by inhibiting the generation of electrophilic oxygen species,while the BAC content improved the selectivity toward propylene by changing the electron cloud density.展开更多
Oxidative dehydrogenation of propane is an attractive route for the synthesis of propylene due to its favorable thermodynamic and kinetic characteristics, however, it is challenging to realize high selectivity towards...Oxidative dehydrogenation of propane is an attractive route for the synthesis of propylene due to its favorable thermodynamic and kinetic characteristics, however, it is challenging to realize high selectivity towards propylene. Recently, it has been discovered that boron nitride (BN) is a promising catalyst that affords superior selectivity towards propylene in oxidative dehydrogenation of propane. Summarizing the progress and unravelling the reaction mechanism of BN in oxidative dehydrogenation of propane are of great significance for the rational design of efficient catalysts in the future. Herein, in this review, the underlying reaction mechanisms of oxidative dehydrogenation of propane over BN are extracted;the developed BN catalysts are classified into pristine BN, functionalized BN, supported BN and others, and the applications of each category of BN catalysts in oxidative dehydrogenation of propane are summarized;the challenges and opportunities on oxidative dehydrogenation of propane over BN are pointed out, aiming to inspire more studies and advance this research field.展开更多
Oxidative dehydrogenation of propane with carbon dioxide(CO_(2)-ODP)characterizes the tandem dehydrogenation of propane to propylene with the reduction of the greenhouse gas of CO_(2)to valuable CO.However,the existin...Oxidative dehydrogenation of propane with carbon dioxide(CO_(2)-ODP)characterizes the tandem dehydrogenation of propane to propylene with the reduction of the greenhouse gas of CO_(2)to valuable CO.However,the existing catalyst is limited due to the poor activity and stability,which hinders its industrialization.Herein,we design the finned Zn-MFI zeolite encapsulated noble metal nanoparticles(NPs)as bifunctional catalysts(NPs@Zn-MFI)for CO_(2)-ODP.Characterization results reveal that the Zn2+species are coordinated with the MFI zeolite matrix as isolated cations and the NPs of Pt,Rh,or Rh Pt are highly dispersed in the zeolite crystals.The isolated Zn2+cations are very effective for activating the propane and the small NPs are favorable for activating the CO_(2),which synergistically promote the selective transformation of propane and CO_(2)to propylene and CO.As a result,the optimal 0.25%Rh0.50%Pt@Zn-MFI catalyst shows the best propylene yield,satisfactory CO_(2)conversion,and long-term stability.Moreover,considering the tunable synergetic effects between the isolated cations and NPs,the developed approach offers a general guideline to design more efficient CO_(2)-ODP catalysts,which is validated by the improved performance of the bifunctional catalysts via simply substituting Sn4+cations for Zn2+cations in the MFI zeolite matrix.展开更多
Pt-based catalysts are the typical industrial catalysts for propane dehydrogenation(PDH),which still suffer from insufficient lo ng-term durability due to the structu ral instability and coke deposition.A commercial ...Pt-based catalysts are the typical industrial catalysts for propane dehydrogenation(PDH),which still suffer from insufficient lo ng-term durability due to the structu ral instability and coke deposition.A commercial γ-Al_(2)O_(3) supported thermally robust sub-nanometer Pt2In3intermetallic catalyst with atomically ordered structure and rigorously separated Pt single atoms was fabricated,which showed outstanding robustness in 240 h long-term operation at 600℃ with the deactivation rate constant kdas low as0.00078 h^(-1), ranking among the lowest reported values.Based on various in situ characterizations and theoretical calculations,it was proved that the catalyst stability not only resulted from the separated Pt single-atom sites but also significantly affected by the distance of adjacent Pt atoms.An increasing distance to 3.25 A in the Pt_(2)In_(3)could induce a weak π-adsorption configuration of propylene on Pt sites,which facilitated the desorption of propylene and restrained the side reactions like coking.展开更多
Highly ordered mesoporous NiMoO4 material was successfully synthesized using mesoporous silica KIT-6 as hard template via vacuum nanocasting method. The structure was characterized by means of XRD, TEM, N2 adsorption-...Highly ordered mesoporous NiMoO4 material was successfully synthesized using mesoporous silica KIT-6 as hard template via vacuum nanocasting method. The structure was characterized by means of XRD, TEM, N2 adsorption-desorption, Raman and FT-IR. The mesoporous NiMoO4 with the coexistence of a-NiMoO4 and fl-NiMoO4 showed well-ordered mesoporous structure, a bimodal pore size distribution and crystalline framework. The catalytic performance of NiMoOa was investigated for oxidative dehydrogenation of propane. It is demonstrated that the mesoporous NiMoO4 catalyst with more surface active oxygen species showed better catalytic performance in oxidative dehydrogena- tion of propane in comparison with bulk NiMoO4.展开更多
The catalytic properties of PtSn-based catalysts supported on siliceous SBA-15 and Al-modified SBA-15, such as Al-incorporated SBA-15 (AlSBA-15) and alumina-modified SBA-15 (Al2O3/SBA-15), for propane dehydrogenat...The catalytic properties of PtSn-based catalysts supported on siliceous SBA-15 and Al-modified SBA-15, such as Al-incorporated SBA-15 (AlSBA-15) and alumina-modified SBA-15 (Al2O3/SBA-15), for propane dehydrogenation were investigated. Al2O3/SBA-15 was prepared either by an impregnation method using aluminum nitrate aqueous solution, or by the treatment of SBA-15 with a Al(OC3H7)3 solution in anhydrous toluene. N2-physisorption, FT-IR spectroscopy, solid-state 27Al MAS NMR spectroscopy, hydrogen chemisorption, XRF, NH3 temperature-programmed desorption, X-ray photoelectron spectroscopy and TPO were used to characterize these samples. Among these catalysts, the PtSn-based catalyst supported on Al2O3/SBA-15, which was grafted with Al(OC3H7)3, exhibited the best catalytic performance in terms of activity and stability The possible reason was due to the high Pt metal dispersion and/or the strong interactions among Pt, Sn, and the support.展开更多
The effect of cerium addition on the catalytic performance of propane dehydrogenation over PtSnNaIZSM-5 catalyst has been investigated by reaction tests and some physicochemical characterization such as XRD, BET, TEM,...The effect of cerium addition on the catalytic performance of propane dehydrogenation over PtSnNaIZSM-5 catalyst has been investigated by reaction tests and some physicochemical characterization such as XRD, BET, TEM, XPS, NH3-TPD, H2 chemisorption, TPR and TPO techniques. It has been found that with suitable amount of cerium addition, the platinum dispersion increased, while the carbon deposition tended to be eliminated easily. In these cases, the presence of cerium could not only realize the better distribution of metallic particles on the support, but also strengthen the interactions between Sn species and the support. Additionally, XPS spectra confirmed that more amounts of tin could exist in oxidized form, which was advantageous to the reaction. In our experiments, PtSnNaCe (1.1 wt%)/ZSM-5 catalyst exhibited the best catalytic performance. After running the reaction for 750 h, propane conversion was maintained higher than 30% with the corresponding selectivity to propylene of about 97%.展开更多
A series of PtCuCeMgAl quintuple hydrotalcite-like compounds with different Ce contents were synthesized by one-pot method. After calcining and reduction, CeO_2-modified Mg(Al)O-supported Pt–Cu alloy catalysts were o...A series of PtCuCeMgAl quintuple hydrotalcite-like compounds with different Ce contents were synthesized by one-pot method. After calcining and reduction, CeO_2-modified Mg(Al)O-supported Pt–Cu alloy catalysts were obtained. To understand the effect of Cu and Ce, the structure and physico-chemistry properties of the catalysts were characterized and analyzed, and the catalytic behaviors were investigated in a direct dehydrogenation of propane to propene. The results show that the Pt^(4+), Cu^(2+), and Ce^(3+) ions can be incorporated into the brucite-like layers and the Ce content significantly affects the interaction strength between Pt and Cu and the dehydrogenation performance of propane. Under the reaction conditions, the highest propane conversion(45%) with 89% selectivity to propene and a 40% propene yield were achieved with a 0.3 wt% Ce-modified PtCu/Mg(Al)O catalyst. The improved catalytic performance is related to the easy formation of Pt–Cu alloy phase, excellent resistance to sintering, and coke deposits of active components modified by CeO_2.展开更多
In this work, a series of Ni-Mo-Mg-O catalysts with mesoporous structure prepared by sol-gel method were investigated for the oxidative dehydrogenation of propane (ODHP). The techniques of temperature-programmed red...In this work, a series of Ni-Mo-Mg-O catalysts with mesoporous structure prepared by sol-gel method were investigated for the oxidative dehydrogenation of propane (ODHP). The techniques of temperature-programmed reduction with H2 (H2-TPR), N2 adsorption-desolption, Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and X-ray photoelectron spectra (XPS) were employed for catalyst characterization. It is found that the activity of the catalysts for ODHP increases first and then decreases with the increase of Mo content. The catalyst with a Mo/Ni atomic ratio of 1/1 exhibits the best catalytic activity, which gives the propene selectivity of 81.4% at a propane conversion of 11.3% under 600 ~C and maintains the good catalytic performance for 22 h on stream. This is related not only to its high reducibility and dispersion as revealed by TPR and XRD, but also to the formation of more selective oxygen species on the MoOz-NiO interface as identified by XPS.展开更多
Propane dehydrogenation(PDH)provides an alternative route to non-petroleum based propylene and eligible catalysts with good overall performance are still being explored.Herein,we report the construction of zeolite sta...Propane dehydrogenation(PDH)provides an alternative route to non-petroleum based propylene and eligible catalysts with good overall performance are still being explored.Herein,we report the construction of zeolite stabilized Pt-Zn catalysts Pt-Zn/Si-Beta for PDH.Characterization results from transmission electron microscopy(TEM),ultraviolet-visible(UV-vis)and Fourier transform infrared(FTIR)spectroscopy reveal that highly-dispersed Zn species are stabilized by the silanols from zeolite framework dealumination,which then act as the anchoring sites for Pt species.The close contact between Pt-Zn species and the electronic interaction thereof make Pt-Zn/Si-Beta robust PDH catalysts.Under optimized conditions,a high propylene production rate of 4.11 molmol_(Pt)^(-1)s^(-1),high propylene selectivity of 98% and a sustainable deactivation rate of~0.02 h^(-1)can be simultaneously achieved at 823 K.Coke deposition is not the key reason for the catalytic deactivation,while the loss of Zn species and the resulting aggregation of Pt species under high temperatures are responsible for the irreversible deactivation of Pt-Zn/Si-Beta catalyst in PDH reaction.展开更多
The reaction kinetics of the oxidative dehydrogenation of propane was studied at 475-550°C over a VMgO catalyst. Vanadium-magnesium-oxides are among the most selective and active catalysts for the dehydrogenation...The reaction kinetics of the oxidative dehydrogenation of propane was studied at 475-550°C over a VMgO catalyst. Vanadium-magnesium-oxides are among the most selective and active catalysts for the dehydrogenation of propane to propylene. Selectivity to propylene up to about 60% was obtained at 10% conversion, but the selectivity decreased with increasing conversion. No oxygenates were detected, the only by-products were CO and CO2. The reaction rate of propane was found to be first order in propane and close to zero order in oxygen, which is in agreement with a Mars van Krevelen mechanism with the activation of the hydrocarbon as the rate determining step. The activation energy of the conversion of propane was found to be 122±6 kJ/mol.展开更多
Alumina materials are widely applied either as a catalyst or support in various industrial catalytic processes. Impurities in alumina that are unfriendly to catalytic performance are inevitably present during the prod...Alumina materials are widely applied either as a catalyst or support in various industrial catalytic processes. Impurities in alumina that are unfriendly to catalytic performance are inevitably present during the production processes. Facing this problem, we here report that the use of sulfur-containing alumina as the support can generate active alumina-supported platinum catalyst, which exhibits superior propylene selectivity and anti-coking ability during propane dehydrogenation. It demonstrated that the sulfur impurity in alumina is not entirely detrimental. During the reduction process, the formation of gas-phase sulfur species increased the electrons and poisoned unsaturated sites of platinum particles. The sulfur impurity in alumina can be removed through a hydrogen reduction process, and the degree of desulfurization is correlated with the operating temperature. This study demonstrated that the rational use of impurity will contribute to the design of a catalyst with high reactivity for potential applications.展开更多
Propane dehydrogenation(PDH), employing Pt-or Cr-based catalysts, represents an emerging industrial route for propylene production. Due to the scarcity of platinum and the toxicity of chromium, alternative PDH catalys...Propane dehydrogenation(PDH), employing Pt-or Cr-based catalysts, represents an emerging industrial route for propylene production. Due to the scarcity of platinum and the toxicity of chromium, alternative PDH catalysts are being pursued. Herein, we report the construction of Zn-containing zeolite catalysts,namely Zn@S-1, for PDH reaction. Well-isolated zinc cations are successfully trapped and stabilized by the Si-OH groups in S-1 zeolites via in-situ hydrothermal synthesis. The as-prepared Zn@S-1 catalysts exhibit good dehydrogenation activity, high propylene selectivity, and regeneration capability in PDH reaction under employed conditions. The in-situ partial reduction of zinc species is observed and the partially reduced zinc cations are definitely identified as the active sites for PDH reaction.展开更多
Propane dehydrogenation(PDH) provides an alternative route for producing propylene. Herein, we demonstrates that h-BN is a promising support of Pt-based catalysts for PDH. The Pt catalysts supported on h-BN were prepa...Propane dehydrogenation(PDH) provides an alternative route for producing propylene. Herein, we demonstrates that h-BN is a promising support of Pt-based catalysts for PDH. The Pt catalysts supported on h-BN were prepared by an impregnation method using Pt(NH_(3))_(4)(NO_(3))_(2) as metal precursors. It has been found that the Pt/BN catalyst undergoing calcination and reduction is highly stable in both PDH reaction and coke-burning regeneration, together with low coke deposition and outstanding propylene selectivity(99%). Detailed characterizations reveal that the high coke resistance and high propylene selectivity of the Pt/BN catalyst are derived not only from the absence of acidity on BN support, but also from the calcination-induced and reduction-adjusted strong metal-support interaction(SMSI) between Pt and BN, which causes the partial encapsulation of Pt particles by BO_(x) overlayers. The BO_(x) overlayers can block the low-coordinated Pt sites and constrain Pt particles into smaller ensembles, suppressing side reactions such as cracking and deep dehydrogenation. Moreover, the BO_(x) overlayers can effectively inhibit Pt sintering by the spatial isolation of Pt during periodic reaction-regeneration cycles. In this work, the catalyst support for PDH is expanded to nonoxide BN, and the understanding of SMSI between Pt and BN will provide rational design strategy for BN-based catalysts.展开更多
The intrinsic kinetics of oxidative dehydrogenation of propane with CO2 has been investigated over Cr/MSU-1 catalyst in a fixed bed reactor. Without limitations of both internal and external diffusion, intrinsic kinet...The intrinsic kinetics of oxidative dehydrogenation of propane with CO2 has been investigated over Cr/MSU-1 catalyst in a fixed bed reactor. Without limitations of both internal and external diffusion, intrinsic kinetic data were obtained under the following conditions: 490-530 °C, space velocity of 3600?6000 mL·h-1·g-1 and 3/1 molar ratio for CO2/C3H8 under normal pressure. Based on Langmuir-Hinshelwood mechanism, the kinetic models were established, and they were validated by statistical analysis. The parameters were estimated using Simplex Method combined with Universal Global Optimization Algorithm. The model, taking the surface reaction process as the rate-determining step, is the best one in agreement with the experimental data.展开更多
Pt-based catalysts are widely used in propane dehydrogenation reaction for the production of propylene.Suppressing irreversible deactivation caused by the sintering of Pt particles under harsh conditions and regenerat...Pt-based catalysts are widely used in propane dehydrogenation reaction for the production of propylene.Suppressing irreversible deactivation caused by the sintering of Pt particles under harsh conditions and regeneration process is a significant challenge in this catalyst.Herein,a series of highly ordered mesoporous Al_(2)O_(3) supports with different levels of Al3+penta sites,are fabricated and used as the support to disperse Pt-Sn_(2) clusters.Characterizations of Pt-Sn_(2)/meso-Al_(2)O_(3) with XRD,NMR,CO-IR,STEM,TG,and Raman techniques along with propane dehydrogenation-regeneration cycles test reveal the structure-stability-re generability relationship.The coordinatively unsaturated pentacoordinate Al_(Al3+penta)^(3+)can strongly anchor Pt atoms via a formation of Al-O-Pt bond,and thus stabilize the Pt-based particles at the surface of Al_(2)O_(3).The stability and regenerability of Pt-Sn2/meso-Al_(2)O_(3) are strongly dependent on the content of Al3+penta sites in the Al_(2)O_(3) structure,and a high level of Al3+penta sites can effectively prevent the agglomeration of Pt-Sn2 clusters into large Pt nanoparticles in the consecutive dehydrogenation-regeneration cycles.The Pt-Sn2/meso-Al_(2)O_(3)-600 with the highest level of Al_(penta)^(3+) (50.8%)delivers the best performance in propane dehydrogenation,which exhibits propane conversion of 40%and propylene selectivity above 98%at 570℃ with 10 vol%C_(3)H_(8) and 10 vol% H_(2) feed.A slow deactivation in this catalyst is ascribed to the formation of coke,and the catalytic performance can be fully restored in the consecutive dehydrogenation-regeneration cycles via a simple calcination treatment.展开更多
A heterogeneous model is developed for the regeneration of the Cr2O3/Al2O3 catalyst for the propane dehydrogenation process by considering the internal mass transfer and external mass/heat transfer during the coke com...A heterogeneous model is developed for the regeneration of the Cr2O3/Al2O3 catalyst for the propane dehydrogenation process by considering the internal mass transfer and external mass/heat transfer during the coke combustion.Simulation shows that under practical operating conditions,multi-steady states exist for the catalyst pellets and the catalyst temperature is sensitive to gas temperature.However,at increased mass flow rate or lowered oxygen concentration,multi-steady states will not appear.Under the strong influences of film diffusion,the coke in the packed bed reactor will first be exhausted at the inlet,while if the film diffusion resistance is decreased,the position of first coke exhaustion moves toward the outlet of the reactor.展开更多
基金This work is supported by the National Natural Science Foundation of China(Grant Nos.21802167,21961132026,92034302,21878331,91645108)the National Key Research and Development Program Nanotechnology Specific Project(No.2020YFA0210903).
文摘Propylene is a significant basic material for petrochemicals such as polypropylene,propylene oxide,etc.With abundant propane supply from shale gas,propane dehydrogenation(PDH)becomes extensively attractive as an on-purpose propylene production route in recent years.Nitrogen-doped carbon(NC)nanopolyhedra supported cobalt catalysts were synthesized in one-step of ZIF-67 pyrolysis and investigated further in PDH.XPS,TEM and N_(2) adsorption-desorption were used to study the influence of carbonization temperature on as-prepared NC supported cobalt catalysts.The temperature is found to affect the cobalt phase and nitrogen species of the catalysts.And the positive correlation was established between Co0 proportion and space time yield of propylene,indicating that the modulation of carbonization temperature could be important for catalytic performance.
基金supported by the Taishan Scholars Program of Shandong Province(tsqn202103051).
文摘Carbon catalysts for propane oxidative dehydrogenation(PODH)can potentially replace metal oxide catalysts due to their environmental friendliness(greenness)and excellent catalytic performance.Biomass carbon materials have the advantages of being abundant in variety,inexpensive,and easily available,but their catalytic selectivity is relatively poor in PODH.Therefore,we report here on a boron-doped sisal fiber carbon catalyst,which showed excellent selectivity of propylene in PODH,excluding the effect of surface-covered B2O3 on the catalytic performance by hot water washing.The carbon material exhibited the best catalytic performance with a load of 2%(mass)and a calcination temperature of 1100℃.At a reaction temperature of 400℃,the conversion rate of propane was 2.0%,and the selectivity toward propylene reached 88.6%.The new chemical bonds formed by boron on the surface of the carbon materials had an important effect on the catalytic performance,as determined by XPS characterization.The BAO groups affected the catalytic activity by inhibiting the generation of electrophilic oxygen species,while the BAC content improved the selectivity toward propylene by changing the electron cloud density.
基金This work received financial support from the National Natural Science Foundation of China(21902116)Scientific Research Foundation of Technology Department of Liaoning province of China(2022-MS-379)Liaoning Revitalization Talents Program(XLYC1902070).
文摘Oxidative dehydrogenation of propane is an attractive route for the synthesis of propylene due to its favorable thermodynamic and kinetic characteristics, however, it is challenging to realize high selectivity towards propylene. Recently, it has been discovered that boron nitride (BN) is a promising catalyst that affords superior selectivity towards propylene in oxidative dehydrogenation of propane. Summarizing the progress and unravelling the reaction mechanism of BN in oxidative dehydrogenation of propane are of great significance for the rational design of efficient catalysts in the future. Herein, in this review, the underlying reaction mechanisms of oxidative dehydrogenation of propane over BN are extracted;the developed BN catalysts are classified into pristine BN, functionalized BN, supported BN and others, and the applications of each category of BN catalysts in oxidative dehydrogenation of propane are summarized;the challenges and opportunities on oxidative dehydrogenation of propane over BN are pointed out, aiming to inspire more studies and advance this research field.
基金supported by the National Natural Science Foundation of China(21902097,21636006 and 21761132025)the China Postdoctoral Science Foundation(2019M653861XB)+1 种基金the Natural Science Foundation of Shaanxi Province(2020JQ-409)the Fundamental Research Funds for the Central Universities(GK201901001 and GK202003035)。
文摘Oxidative dehydrogenation of propane with carbon dioxide(CO_(2)-ODP)characterizes the tandem dehydrogenation of propane to propylene with the reduction of the greenhouse gas of CO_(2)to valuable CO.However,the existing catalyst is limited due to the poor activity and stability,which hinders its industrialization.Herein,we design the finned Zn-MFI zeolite encapsulated noble metal nanoparticles(NPs)as bifunctional catalysts(NPs@Zn-MFI)for CO_(2)-ODP.Characterization results reveal that the Zn2+species are coordinated with the MFI zeolite matrix as isolated cations and the NPs of Pt,Rh,or Rh Pt are highly dispersed in the zeolite crystals.The isolated Zn2+cations are very effective for activating the propane and the small NPs are favorable for activating the CO_(2),which synergistically promote the selective transformation of propane and CO_(2)to propylene and CO.As a result,the optimal 0.25%Rh0.50%Pt@Zn-MFI catalyst shows the best propylene yield,satisfactory CO_(2)conversion,and long-term stability.Moreover,considering the tunable synergetic effects between the isolated cations and NPs,the developed approach offers a general guideline to design more efficient CO_(2)-ODP catalysts,which is validated by the improved performance of the bifunctional catalysts via simply substituting Sn4+cations for Zn2+cations in the MFI zeolite matrix.
基金financially supported by the DNL Cooperation Fund,CAS (DNL202002)the National Natural Science Foundation of China (22102180)+3 种基金the CAS Project for Young Scientists in Basic Research,(YSBR-022)the Key Research Program of Frontier Sciences,CAS (ZDBS-LY-7012)Liao Ning Revitalization Talents Program (XLYC2007070)the Fundamental Research Funds for the Central Universities (20720220009)。
文摘Pt-based catalysts are the typical industrial catalysts for propane dehydrogenation(PDH),which still suffer from insufficient lo ng-term durability due to the structu ral instability and coke deposition.A commercial γ-Al_(2)O_(3) supported thermally robust sub-nanometer Pt2In3intermetallic catalyst with atomically ordered structure and rigorously separated Pt single atoms was fabricated,which showed outstanding robustness in 240 h long-term operation at 600℃ with the deactivation rate constant kdas low as0.00078 h^(-1), ranking among the lowest reported values.Based on various in situ characterizations and theoretical calculations,it was proved that the catalyst stability not only resulted from the separated Pt single-atom sites but also significantly affected by the distance of adjacent Pt atoms.An increasing distance to 3.25 A in the Pt_(2)In_(3)could induce a weak π-adsorption configuration of propylene on Pt sites,which facilitated the desorption of propylene and restrained the side reactions like coking.
基金supported by NSFC(21073235,21173270,21177160,21376261)863 Program(2013AA065302)PetroChina Innovation Foundation(2011D-5006-0403)
文摘Highly ordered mesoporous NiMoO4 material was successfully synthesized using mesoporous silica KIT-6 as hard template via vacuum nanocasting method. The structure was characterized by means of XRD, TEM, N2 adsorption-desorption, Raman and FT-IR. The mesoporous NiMoO4 with the coexistence of a-NiMoO4 and fl-NiMoO4 showed well-ordered mesoporous structure, a bimodal pore size distribution and crystalline framework. The catalytic performance of NiMoOa was investigated for oxidative dehydrogenation of propane. It is demonstrated that the mesoporous NiMoO4 catalyst with more surface active oxygen species showed better catalytic performance in oxidative dehydrogena- tion of propane in comparison with bulk NiMoO4.
基金supported by the National Nature Science Foundation of China (50873026, 21106017)the Production and Research Prospective Joint Research Project (BY2009153)+1 种基金the Science and Technology Support Program (BE2008129) of Jiangsu Province of ChinaSpecialized Research Fund for the Doctoral Program of Higher Education of China (20100092120047)
文摘The catalytic properties of PtSn-based catalysts supported on siliceous SBA-15 and Al-modified SBA-15, such as Al-incorporated SBA-15 (AlSBA-15) and alumina-modified SBA-15 (Al2O3/SBA-15), for propane dehydrogenation were investigated. Al2O3/SBA-15 was prepared either by an impregnation method using aluminum nitrate aqueous solution, or by the treatment of SBA-15 with a Al(OC3H7)3 solution in anhydrous toluene. N2-physisorption, FT-IR spectroscopy, solid-state 27Al MAS NMR spectroscopy, hydrogen chemisorption, XRF, NH3 temperature-programmed desorption, X-ray photoelectron spectroscopy and TPO were used to characterize these samples. Among these catalysts, the PtSn-based catalyst supported on Al2O3/SBA-15, which was grafted with Al(OC3H7)3, exhibited the best catalytic performance in terms of activity and stability The possible reason was due to the high Pt metal dispersion and/or the strong interactions among Pt, Sn, and the support.
基金supported by the National Natural Science Foundation of China (Grant No. 50873026 and 21106017)the Production and Research Prospective Joint Research Project of Jiangsu Province of China (Grant No. BY2009153)the Specialized Research Fund for the Doctoral Program of Higher Education of China (Grant No. 20100092120047)
文摘The effect of cerium addition on the catalytic performance of propane dehydrogenation over PtSnNaIZSM-5 catalyst has been investigated by reaction tests and some physicochemical characterization such as XRD, BET, TEM, XPS, NH3-TPD, H2 chemisorption, TPR and TPO techniques. It has been found that with suitable amount of cerium addition, the platinum dispersion increased, while the carbon deposition tended to be eliminated easily. In these cases, the presence of cerium could not only realize the better distribution of metallic particles on the support, but also strengthen the interactions between Sn species and the support. Additionally, XPS spectra confirmed that more amounts of tin could exist in oxidized form, which was advantageous to the reaction. In our experiments, PtSnNaCe (1.1 wt%)/ZSM-5 catalyst exhibited the best catalytic performance. After running the reaction for 750 h, propane conversion was maintained higher than 30% with the corresponding selectivity to propylene of about 97%.
基金supported by the National Natural Science Foundation of China(No.21776214)the Natural Science Foundation of Jiangsu Province(No.BK20161166)the State Key Laboratory of Chemical Resource Engineering
文摘A series of PtCuCeMgAl quintuple hydrotalcite-like compounds with different Ce contents were synthesized by one-pot method. After calcining and reduction, CeO_2-modified Mg(Al)O-supported Pt–Cu alloy catalysts were obtained. To understand the effect of Cu and Ce, the structure and physico-chemistry properties of the catalysts were characterized and analyzed, and the catalytic behaviors were investigated in a direct dehydrogenation of propane to propene. The results show that the Pt^(4+), Cu^(2+), and Ce^(3+) ions can be incorporated into the brucite-like layers and the Ce content significantly affects the interaction strength between Pt and Cu and the dehydrogenation performance of propane. Under the reaction conditions, the highest propane conversion(45%) with 89% selectivity to propene and a 40% propene yield were achieved with a 0.3 wt% Ce-modified PtCu/Mg(Al)O catalyst. The improved catalytic performance is related to the easy formation of Pt–Cu alloy phase, excellent resistance to sintering, and coke deposits of active components modified by CeO_2.
基金supported by the National Natural Science Foundation of China (20776089)the New Century Excellent Talent Project of China(NCET-05-0783)
文摘In this work, a series of Ni-Mo-Mg-O catalysts with mesoporous structure prepared by sol-gel method were investigated for the oxidative dehydrogenation of propane (ODHP). The techniques of temperature-programmed reduction with H2 (H2-TPR), N2 adsorption-desolption, Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and X-ray photoelectron spectra (XPS) were employed for catalyst characterization. It is found that the activity of the catalysts for ODHP increases first and then decreases with the increase of Mo content. The catalyst with a Mo/Ni atomic ratio of 1/1 exhibits the best catalytic activity, which gives the propene selectivity of 81.4% at a propane conversion of 11.3% under 600 ~C and maintains the good catalytic performance for 22 h on stream. This is related not only to its high reducibility and dispersion as revealed by TPR and XRD, but also to the formation of more selective oxygen species on the MoOz-NiO interface as identified by XPS.
基金supported by the Municipal Natural Science Foundation of Tianjin(18JCJQJC47400,18JCZDJC37400)the National Postdoctoral Program for Innovative Talent(BX20200171)the Fundamental Research Funds for the Central Universities。
文摘Propane dehydrogenation(PDH)provides an alternative route to non-petroleum based propylene and eligible catalysts with good overall performance are still being explored.Herein,we report the construction of zeolite stabilized Pt-Zn catalysts Pt-Zn/Si-Beta for PDH.Characterization results from transmission electron microscopy(TEM),ultraviolet-visible(UV-vis)and Fourier transform infrared(FTIR)spectroscopy reveal that highly-dispersed Zn species are stabilized by the silanols from zeolite framework dealumination,which then act as the anchoring sites for Pt species.The close contact between Pt-Zn species and the electronic interaction thereof make Pt-Zn/Si-Beta robust PDH catalysts.Under optimized conditions,a high propylene production rate of 4.11 molmol_(Pt)^(-1)s^(-1),high propylene selectivity of 98% and a sustainable deactivation rate of~0.02 h^(-1)can be simultaneously achieved at 823 K.Coke deposition is not the key reason for the catalytic deactivation,while the loss of Zn species and the resulting aggregation of Pt species under high temperatures are responsible for the irreversible deactivation of Pt-Zn/Si-Beta catalyst in PDH reaction.
文摘The reaction kinetics of the oxidative dehydrogenation of propane was studied at 475-550°C over a VMgO catalyst. Vanadium-magnesium-oxides are among the most selective and active catalysts for the dehydrogenation of propane to propylene. Selectivity to propylene up to about 60% was obtained at 10% conversion, but the selectivity decreased with increasing conversion. No oxygenates were detected, the only by-products were CO and CO2. The reaction rate of propane was found to be first order in propane and close to zero order in oxygen, which is in agreement with a Mars van Krevelen mechanism with the activation of the hydrocarbon as the rate determining step. The activation energy of the conversion of propane was found to be 122±6 kJ/mol.
基金supported by the National Key Research and Development Project(2018YFA0209404)the State Key Program of the National Natural Science Foundation of China(21733002)the National Natural Science Foundation of China(U1908203)。
文摘Alumina materials are widely applied either as a catalyst or support in various industrial catalytic processes. Impurities in alumina that are unfriendly to catalytic performance are inevitably present during the production processes. Facing this problem, we here report that the use of sulfur-containing alumina as the support can generate active alumina-supported platinum catalyst, which exhibits superior propylene selectivity and anti-coking ability during propane dehydrogenation. It demonstrated that the sulfur impurity in alumina is not entirely detrimental. During the reduction process, the formation of gas-phase sulfur species increased the electrons and poisoned unsaturated sites of platinum particles. The sulfur impurity in alumina can be removed through a hydrogen reduction process, and the degree of desulfurization is correlated with the operating temperature. This study demonstrated that the rational use of impurity will contribute to the design of a catalyst with high reactivity for potential applications.
基金National Natural Science Fund of China(22025203, 21872072)the Municipal Natural Science Fund of Tianjin (18JCJQJC47400) for supporting the work。
文摘Propane dehydrogenation(PDH), employing Pt-or Cr-based catalysts, represents an emerging industrial route for propylene production. Due to the scarcity of platinum and the toxicity of chromium, alternative PDH catalysts are being pursued. Herein, we report the construction of Zn-containing zeolite catalysts,namely Zn@S-1, for PDH reaction. Well-isolated zinc cations are successfully trapped and stabilized by the Si-OH groups in S-1 zeolites via in-situ hydrothermal synthesis. The as-prepared Zn@S-1 catalysts exhibit good dehydrogenation activity, high propylene selectivity, and regeneration capability in PDH reaction under employed conditions. The in-situ partial reduction of zinc species is observed and the partially reduced zinc cations are definitely identified as the active sites for PDH reaction.
基金financially supported by the National Natural Science Foundation of China(21273049,22172037)the Guangdong Basic and Applied Basic Research Foundation(2021A1515010014)+1 种基金the Science and Technology Program of Guangzhou(201904010023)the CAS Key Laboratory of Renewable Energy(E029kf0901)。
文摘Propane dehydrogenation(PDH) provides an alternative route for producing propylene. Herein, we demonstrates that h-BN is a promising support of Pt-based catalysts for PDH. The Pt catalysts supported on h-BN were prepared by an impregnation method using Pt(NH_(3))_(4)(NO_(3))_(2) as metal precursors. It has been found that the Pt/BN catalyst undergoing calcination and reduction is highly stable in both PDH reaction and coke-burning regeneration, together with low coke deposition and outstanding propylene selectivity(99%). Detailed characterizations reveal that the high coke resistance and high propylene selectivity of the Pt/BN catalyst are derived not only from the absence of acidity on BN support, but also from the calcination-induced and reduction-adjusted strong metal-support interaction(SMSI) between Pt and BN, which causes the partial encapsulation of Pt particles by BO_(x) overlayers. The BO_(x) overlayers can block the low-coordinated Pt sites and constrain Pt particles into smaller ensembles, suppressing side reactions such as cracking and deep dehydrogenation. Moreover, the BO_(x) overlayers can effectively inhibit Pt sintering by the spatial isolation of Pt during periodic reaction-regeneration cycles. In this work, the catalyst support for PDH is expanded to nonoxide BN, and the understanding of SMSI between Pt and BN will provide rational design strategy for BN-based catalysts.
基金supported by the National Natural Science Foundation of China (No. 21006109)the Postdoctoral Science Foundation of China (No. 20080430581)the CASKC Wang Post-Doctoral Fellowship
文摘The intrinsic kinetics of oxidative dehydrogenation of propane with CO2 has been investigated over Cr/MSU-1 catalyst in a fixed bed reactor. Without limitations of both internal and external diffusion, intrinsic kinetic data were obtained under the following conditions: 490-530 °C, space velocity of 3600?6000 mL·h-1·g-1 and 3/1 molar ratio for CO2/C3H8 under normal pressure. Based on Langmuir-Hinshelwood mechanism, the kinetic models were established, and they were validated by statistical analysis. The parameters were estimated using Simplex Method combined with Universal Global Optimization Algorithm. The model, taking the surface reaction process as the rate-determining step, is the best one in agreement with the experimental data.
基金Financial supports of the National Natural Science Foundation of China(21878050,91934301)the State Key Laboratory of Coal Conversion(J21-22-620)the 111 Project(D17005)。
文摘Pt-based catalysts are widely used in propane dehydrogenation reaction for the production of propylene.Suppressing irreversible deactivation caused by the sintering of Pt particles under harsh conditions and regeneration process is a significant challenge in this catalyst.Herein,a series of highly ordered mesoporous Al_(2)O_(3) supports with different levels of Al3+penta sites,are fabricated and used as the support to disperse Pt-Sn_(2) clusters.Characterizations of Pt-Sn_(2)/meso-Al_(2)O_(3) with XRD,NMR,CO-IR,STEM,TG,and Raman techniques along with propane dehydrogenation-regeneration cycles test reveal the structure-stability-re generability relationship.The coordinatively unsaturated pentacoordinate Al_(Al3+penta)^(3+)can strongly anchor Pt atoms via a formation of Al-O-Pt bond,and thus stabilize the Pt-based particles at the surface of Al_(2)O_(3).The stability and regenerability of Pt-Sn2/meso-Al_(2)O_(3) are strongly dependent on the content of Al3+penta sites in the Al_(2)O_(3) structure,and a high level of Al3+penta sites can effectively prevent the agglomeration of Pt-Sn2 clusters into large Pt nanoparticles in the consecutive dehydrogenation-regeneration cycles.The Pt-Sn2/meso-Al_(2)O_(3)-600 with the highest level of Al_(penta)^(3+) (50.8%)delivers the best performance in propane dehydrogenation,which exhibits propane conversion of 40%and propylene selectivity above 98%at 570℃ with 10 vol%C_(3)H_(8) and 10 vol% H_(2) feed.A slow deactivation in this catalyst is ascribed to the formation of coke,and the catalytic performance can be fully restored in the consecutive dehydrogenation-regeneration cycles via a simple calcination treatment.
基金Supported by the National Natural Science Foundation of China(20736011) the Ministry of Education of China(IRT0721)
文摘A heterogeneous model is developed for the regeneration of the Cr2O3/Al2O3 catalyst for the propane dehydrogenation process by considering the internal mass transfer and external mass/heat transfer during the coke combustion.Simulation shows that under practical operating conditions,multi-steady states exist for the catalyst pellets and the catalyst temperature is sensitive to gas temperature.However,at increased mass flow rate or lowered oxygen concentration,multi-steady states will not appear.Under the strong influences of film diffusion,the coke in the packed bed reactor will first be exhausted at the inlet,while if the film diffusion resistance is decreased,the position of first coke exhaustion moves toward the outlet of the reactor.