Catalytic epoxidation of alkenes is an important type of organic reaction in chemical industry,and the deep insight into catalyst deactivation will help to develop new epoxidation process.In this work,series of quater...Catalytic epoxidation of alkenes is an important type of organic reaction in chemical industry,and the deep insight into catalyst deactivation will help to develop new epoxidation process.In this work,series of quaternary ammoniums bearing different cationic sizes,i.e.MTOA+(methyltrioctylammonium,[(C_(8)H_(17))_(3)CH_(3)N]+),HTMA+(hexadecyltrimethylammonium,[(C_(16)H_(33))(CH_(3))_(3)N]+) and DMDOA+(dimethyldioctadecylammonium,[(C_(18)H_(37))_(2)(CH_(3))_(2)N]+) were incorporated with polyoxometalate (POM) anions to prepare phase transfer catalysts (PTCs),which were used in the styrene epoxidations.Among them,(MTOA)_(3)PW_(4)O_(24)exhibits the best catalytic performance judged from the highest styrene conversion rate(52%) and styrene oxide selectivity (93%),during which the styrene epoxidation conditions were optimized.Meanwhile,the deactivation mechanism of this kind of PTCs was proposed firstly,i.e.in the case of low H_(2)O_(2) content,the oxidant can only be used in the styrene epoxidation,in which the catalyst can transform into stable Keggin-type POM.But when the content of H_(2)O_(2) is higher,the excess H_(2)O_(2) can reactivate the Keggin-type POM into active (PW_(4)O_(24))_(3)-anions,which can trigger the ring-opening polymerization of styrene oxide.Consequently,the catalyst is deactivated by adhered poly(styrene oxide)irreversibly,which was determined by NMR spectra.In this situation,the active moiety{PO_(4)[WO(O_(2))_(2)]_(4)}_(3)-in phase-transfer catalytic system can break into some unidentified species with low W/P ratio with the presence of epoxides.This work will be beneficial for the design of new PTCs in alkene epoxidation in fine chemical industry.展开更多
How catalyst shape affects its deactivation is a crucial issue for quickly decaying catalysts such as zeolite in 2-butene and isobutane alkylation.In this work,steady simulations are used to determine the temperature ...How catalyst shape affects its deactivation is a crucial issue for quickly decaying catalysts such as zeolite in 2-butene and isobutane alkylation.In this work,steady simulations are used to determine the temperature and species distribution in fixed beds filled with particles of four shapes.Subsequently,unsteady simulations are used to study the deactivation behavior of the catalysts based on the steady simulation results.We describe the deactivation rate and type of catalyst deactivation by defining a local internal diffusivity,which is affected by catalytic activity.The results reveal that the internal diffusion distance of the catalyst determines the deactivation rate,whereas the local internal diffusivity determines its deactivation type.展开更多
The kinetics of propane dehydrogenation and catalyst deactivation over Pt-Sn/Al2O3 catalyst were studied.Performance test runs were carried out in a fixed-bed integral reactor.Using a power-law rate expression for the...The kinetics of propane dehydrogenation and catalyst deactivation over Pt-Sn/Al2O3 catalyst were studied.Performance test runs were carried out in a fixed-bed integral reactor.Using a power-law rate expression for the surface reaction kinetics and independent law for deactivation kinetics,the experimental data were analyzed both by integral and a novel differential method of analysis and the results were compared.To avoid fluctuation of time-derivatives of conversion required for differential analysis,the conversion-time data were first fitted with appropriate functions.While the time-zero and rate constant of reaction were largely insensitive to the function employed,the rate constant of deactivation was much more sensitive to the function form.The advantage of the proposed differential method,however,is that the integration of the rate expression is not necessary which otherwise could be complicated or impossible.It was also found that the reaction is not limited by external and internal mass transfer limitations,implying that the employed kinetics could be considered as intrinsic ones.展开更多
A series of model catalysts were obtained by treating commercial fresh and spent catalysts unloaded from the factory with different methods, including green oil dipping, extraction and high-temperature regeneration;fi...A series of model catalysts were obtained by treating commercial fresh and spent catalysts unloaded from the factory with different methods, including green oil dipping, extraction and high-temperature regeneration;finally, the deactivation behavior of the commercial catalyst for acetylene hydrogenation were studied. The influence of various possible deactivation factors on the catalytic performance was elucidated via detailed structural characterization, surface composition analysis, and activity evaluation.The results showed that green oil, carbon deposit and sintering of active metal were the main reasons for deactivation, among which green oil and carbon deposit led to rapid deactivation, while the activity could be recovered after regeneration by high-temperature calcination. The sintering of active metal components was attributed to the high-temperature regeneration in hydrothermal conditions, which was slow but irreversible and accounted for permanent deactivation. Thus, optimizing the regeneration is expected to extend the service life of the commercial catalyst.展开更多
The selective aqueous-phase glycerol hydrogenolysis is a promising reaction to produce commercially useful 1,3-propanediol(1,3-PDO).The Pt-WOx bifunctional catalyst can catalyse the glycerol hydrogenol-ysis but the ca...The selective aqueous-phase glycerol hydrogenolysis is a promising reaction to produce commercially useful 1,3-propanediol(1,3-PDO).The Pt-WOx bifunctional catalyst can catalyse the glycerol hydrogenol-ysis but the catalyst deactivation via sintering,metal leaching,and coking can predominantly occur in the aqueous phase reaction.In this work,the effect of reaction temperature,pressure and second promoter(Cu,Fe,Rh,Mn,Re,Ru,Ir,Sn,B,and P)on catalytic performance and deactivation behaviour of Pt/WOx/-Al2O3 was investigated.When doped with Rh,Mn,Re,Ru,Ir,B,and P,the second promoter boosts catalytic activity by promoting great dispersion of Pt on support and increasing Pt surface area.The increased Bronsted acid sites lead to selective synthesis of 1,3-PDO than 1,2-propanediol(1,2-PDO).The characterization studies of fresh and spent catalysts reveal that the main cause of catalyst deactivation is the Pt sintering,as interpreted based on XRD,CO chemisorption,and TEM analyses.The Pt sintering is affected depending on the second promoter that can either or reduce the interaction between Pt,WO_(χ)/γ and Al_(2)O_(3).As an electron acceptor of Pt in Pt/WO_(χ)/γ-Al_(2)O_(3),Re and Mn as second promoters resulted in increased Pt^(2+) on the catalytic surface,which strengthens the contact between Pt andγ-Al_(2)O_(3) and WO_(χ),resulting in a decrease in Pt sintering.The metal leaching and coking are not affected by the presence of second promoter.The catalyst modified with a second promoter possesses improved catalytic activity and 1,3-PDO production,however the stability continues to remain a challenge.The present work unrav-elled the determining parameters of catalytic activity and deactivation,thus providing a promising pro-tocol toward effective catalysts for glycerol hydrogenolysis.展开更多
Chlorotrifluoroethylene(CTFE)is a vital fluorinated olefinic monomer produced through the catalytic hydrodechlorination of trichlorotrifluoroethane(CFC-113),an eco-friendly process.However,hydrodechlorination catalyst...Chlorotrifluoroethylene(CTFE)is a vital fluorinated olefinic monomer produced through the catalytic hydrodechlorination of trichlorotrifluoroethane(CFC-113),an eco-friendly process.However,hydrodechlorination catalysts for olefin production often suffer from poor stability.The Pd/AC catalyst and Pd-Cu/AC catalyst prepared by co-impregnation method exhibited poor stability,Pd-Cu/AC catalyst with CFC-113 conversion dropping to around 37%after 50 h of hydrodechlorination reaction.Brunauer-Emmett-Teller,transmission electron microscopy,X-ray photoelectron spectroscopy,and X-ray diffraction of fresh and deactivated Pd/AC catalysts indicate that the deactivation of Pd/AC catalysts is due to high-temperature agglomeration of Pd.Comparative analysis of fresh and deactivated Pd-Cu/AC catalysts using Brunauer-Emmett-Teller,transmission electron microscopy,and thermogravimetric analysis techniques revealed decreased dispersion of active sites,reduced surface area,catalyst aggregation deactivation,and a significant decrease in Cu content.Furthermore,the results of NH3-TPD revealed that the acid sites of the catalyst increased significantly.X-ray diffraction spectra indicated the formation of new species,basic copper chloride(Cu_(2)(OH)_(3)Cl),during the reaction.As the reaction progressed,these new species agglomerated,leading to a gradual loss of catalyst activity.Moreover,the deactivated catalyst was successfully reactivated using a simple alkaline washing method.展开更多
The alkylation of benzene with isopropanol over beta-zeolite is a more cost-effective solution to cumene production. During the benzene alkylation cycles, the cumene selectivity slowly increased, while the benzene con...The alkylation of benzene with isopropanol over beta-zeolite is a more cost-effective solution to cumene production. During the benzene alkylation cycles, the cumene selectivity slowly increased, while the benzene conversion presented the sharp decrease due to catalyst deactivation. The deactivation mechanism of betazeolite catalyst was investigated by characterizing the fresh and used catalysts. The XRD, SEM and TEM results show that the crystalline and particle size of the beta-zeolite catalyst almost remained stable during the alkylation cycles. The drop in catalytic activity and benzene conversion could be explained by the TG, BET,NH_3-TPD and GC–MS results. The organic matters mainly consisted of ethylbenzene, p-xylene and 1-ethyl-3-(1-methyl) benzene produced in the benzene alkylation deposited in the catalyst, which strongly reduced the specific surface area of beta-zeolite catalyst. Moreover, during the reaction cycles, the amount of acidity also significantly decreased. As a result, the catalyst deactivation occurred. To maintain the catalytic performance,the catalyst regeneration was carried out by using ethanol rinse and calcination. The deactivated catalyst could be effectively regenerated by the calcination method and the good catalytic performance was obtained.展开更多
A physical mixture of alkali-promoted iron catalyst with binder based on Fischer-Tropsch synthesis and an acidic co-catalyst (HZSM5) for syngas conversion to hydrocarbons was studied in a fixed bed micro reactor. De...A physical mixture of alkali-promoted iron catalyst with binder based on Fischer-Tropsch synthesis and an acidic co-catalyst (HZSM5) for syngas conversion to hydrocarbons was studied in a fixed bed micro reactor. Deactivation data were obtained during the synthesis over a 1400 h period. The deactivation studies on iron catalyst showed that this trend followed the phase transformation Fe2.2C ( ε′) → Fe5C2 (χ) → Fe3C (θ), and the final predominant phase of the catalyst was Fe3C (θ). Deactivation of zeolite component in bifunctional catalyst may be caused by coking over the zeolitic component, dealumination of zeolite crystals, and migration of alkali promoters from iron catalyst under synthesis conditions. The deactivation rate of iron catalyst was also obtained.展开更多
A nano-structured iron catalyst for syngas conversion to hydrocarbons in Fischer-Tropsch synthesis(FTS) was prepared by micro-emulsion method.Compositions of bulk iron phase and phase transformations of carbonaceous...A nano-structured iron catalyst for syngas conversion to hydrocarbons in Fischer-Tropsch synthesis(FTS) was prepared by micro-emulsion method.Compositions of bulk iron phase and phase transformations of carbonaceous species during catalyst deactivation in FTS reaction were characterized by temperature-programmed surface reaction with hydrogen(TPSR-H 2 ),and XRD techniques.Many carbonaceous species on surface and bulk of the nano-structured iron catalysts were completely identified by combined TPSR-H 2 and XRD spectra and which were compared with those recorded on conventional co-precipitated iron catalyst.The results reveal that the catalyst deactivation results from the formation of inactive carbide phases and surface carbonaceous species like graphite,and it will be increased when the particle size of iron oxides was reduced in FTS iron catalyst.展开更多
Nickel, cobalt, copper and platinum nanoparticles supported on carbon nano-fibers were evaluated with respect to their stability, catalytic activity and selectivity in the aqueous phase reforming of ethylene glycol (...Nickel, cobalt, copper and platinum nanoparticles supported on carbon nano-fibers were evaluated with respect to their stability, catalytic activity and selectivity in the aqueous phase reforming of ethylene glycol (230 ℃, autogenous pressure, batch reactor). The initial surface-specific activities for ethylene glycol reforming were in a similar range but decreased in the order of Pt (15.5 h-1 ) 〉Co(13.0 h 1 ) 〉Ni(5.2 h-1) while the Cu catalyst only showed low dehydrogenation activity. The hydrogen molar selectivity decreased in the order of Pt (53%)〉Co(21%)〉Ni (15%) as a result of the production of methane over the latter two catalysts. Over the Co catalyst acids were formed in the liquid phase while alcohols were formed over Ni and Pt. Due to the low pH of the reaction mixture, especially in the case of Co (as a result of the formed acids), significant cobalt leaching occurs which resulted in a rapid deactivation of this catalyst. Investigations of the spent catalysts with various techniques showed that metal particle growth is responsible for the deactivation of the Pt and Ni catalysts. In addition, coking might also contribute to the deactivation of the Ni catalyst.展开更多
The effect of polycyclic aromatic hydrocarbons(PAHs)on the stability of the hydrogenation catalyst for production of ultra-low sulfur diesel was studied in a pilot plant using Ni-Mo-W/γ-Al_(2)O_(3)catalyst.The mechan...The effect of polycyclic aromatic hydrocarbons(PAHs)on the stability of the hydrogenation catalyst for production of ultra-low sulfur diesel was studied in a pilot plant using Ni-Mo-W/γ-Al_(2)O_(3)catalyst.The mechanisms of catalyst deactivation were analyzed by the methods of elemental analysis,nitrogen adsorption-desorption,thermogravimetry-mass spectrometry(TG-MS)technology,X-ray photoelectron spectroscopy(XPS)and high resolution transmission electron microscopy(HRTEM).The results demonstrated that PAHs had little effect on the activity of catalyst at the beginning of operation,during which the reaction temperature was increased by only 1-4℃.However,the existence of PAHs significantly accelerated the deactivation of catalyst and weakened the stability of catalyst.This phenomenon could be explained by the reason that the catalyst deactivation is not only related to the formation of carbon deposit,but is also closely related to the loss of pore volume and the decrease of Ni-W-S phase ratio after adding PAHs.展开更多
Cobalt supported on carbon nanotubes (CNTs)-covered alumina has been recently developed and successfully utilized as a catalyst in Fischer-Tropsch synthesis (FTS). Problems associated with shaping of Co/CNTs into ...Cobalt supported on carbon nanotubes (CNTs)-covered alumina has been recently developed and successfully utilized as a catalyst in Fischer-Tropsch synthesis (FTS). Problems associated with shaping of Co/CNTs into extrudates or pellets as well as catalyst attrition rendered these materials unfavorable for industrial applications. In this investigation regular γ- and nano-structured (N-S) alumina as well as CNTs-covered regular γ- and N-S-alumina supports were impregnated by cobalt nitrate solution to make new cobalt-based catalysts which were also promoted by Ru. The catalysts were characterized and tested in a micro reactor to evaluate their applicability in FTS. γ-Al2O3 was prepared by calcination of bohemite and N-S-Al2O3 was prepared by sol-gel method using aluminum chloride as starting material. Catalyst evaluations indicated that N-S-Al2O3 was superior to regular γ-Al2O3 and that CNTs-covered alumina supports were favored over non-covered ones in terms of activity and heavy hydrocarbon selectivity. These were justified by porosimetric characteristics of the catalysts and existence of CNTs points of view. CNTs-covered catalysts also showed higher wax selectivity and better resistance to deactivation. Furthermore, TPR analysis indicated that the cobalt aluminate phase, which is responsible for the permanent deactivation of alumina supported Co-based catalysts, did not form on alumina supported Co-based catalysts covered with CNTs due to weaker interactions between cobalt and alumina.展开更多
Low-carbon process for resource utilization of polycyclic aromatic hydrocarbons(PAHs)in zeolitecatalyzed processes,geared to carbon neutrality-a prominent trend throughout human activities,has been bottlenecked by the...Low-carbon process for resource utilization of polycyclic aromatic hydrocarbons(PAHs)in zeolitecatalyzed processes,geared to carbon neutrality-a prominent trend throughout human activities,has been bottlenecked by the lack of a complete mechanistic understanding of coking and decoking chemistry,involving the speciation and molecular evolution of PAHs,the plethora of which causes catalyst deactivation and forces regeneration,rendering significant CO_(2) emission.Herein,by exploiting the high-resolution matrix-assisted laser desorption/ionization Fourier-transform ion cyclotron resonance mass spectrometry(MALDI FT-ICR MS),we unveil the missing fingerprints of the mechanistic pathways for both formation and decomposition of cross-linked cage-passing PAHs for SAPO-34-catalyzed,industrially relevant methanol-to-olefins(MTO)as a model reaction.Notable is the molecule-resolved symmetrical signature:their speciation originates exclusively from the direct coupling of in-cage hydrocarbon pool(HCP)species,whereas water-promoted decomposition of cage-passing PAHs initiates with selective cracking of inter-cage local structures at 8-rings followed by deep aromatic steam reforming.Molecular deciphering the reversibly dynamic evolution trajectory(fate)of full-spectrum aromatic hydrocarbons and fulfilling the real-time quantitative carbon resource footprints advance the fundamental knowledge of deactivation and regeneration phenomena(decay and recovery motifs of autocatalysis)and disclose the underlying mechanisms of especially the chemistry of coking and decoking in zeolite catalysis.The positive yet divergent roles of water in these two processes are disentangled.These unprecedented insights ultimately lead us to a steam regeneration strategy with valuable CO and H_(2) as main products,negligible CO_(2) emission in steam reforming and full catalyst activity recovery,which further proves feasible in other important chemical processes,promising to be a sustainable and potent approach that contributes to carbon-neutral chemical industry.展开更多
Dehydrogenation of ethylbenzene (EB) to styrene (ST) in the presence of CO2, in which EB dehydrogenation is coupled with the reverse water-gas shift (RWGS), was investigated extensively through both theoretical ...Dehydrogenation of ethylbenzene (EB) to styrene (ST) in the presence of CO2, in which EB dehydrogenation is coupled with the reverse water-gas shift (RWGS), was investigated extensively through both theoretical analysis and experimental characterization. The reaction coupling proved to be superior to the single dehydrogenation in several respects. Thermodynamic analysis suggests that equilibrium conversion of EB can be improved greatly by reaction coupling due to the simultaneous elimination of the hydrogen produced from dehydrogenation. Catalytic tests proved that iron and vanadium supported on activated carbon or Al2O3 with certain promoters are potential catalysts for this coupling process. The catalysts of iron and vanadium are different in the reaction mechanism, although ST yield is always associated with CO2 conversion over various catalysts. The two-step pathway plays an important role in the coupling process over Fe/Al2O3, while the one-step pathway dominates the reaction over V/Al2O3. Coke deposition and deep reduction of active components are the major causes of catalyst deactivation. CO2 can alleviate the catalyst deactivation effectively through preserving the active species at high valence in the coupling process, though it can not suppress the coke deposition.展开更多
The RTS technology can produce ultra-low sulfur diesel at lower costs using available hydrogenation catalyst and device.However,with the increase of the mixing proportion of secondary processed diesel fuel in the feed...The RTS technology can produce ultra-low sulfur diesel at lower costs using available hydrogenation catalyst and device.However,with the increase of the mixing proportion of secondary processed diesel fuel in the feed,the content of nitrogen compounds and polycyclic aromatic hydrocarbons in the feed increased,leading to the acceleration of the deactivation rate of the primary catalyst and the shortening of the service cycle.In order to fully understand the reason of catalyst deactivation,the effect of mixing secondary processed diesel fuel oil on the operating stability of the catalyst in the first reactor was investigated in a medium-sized fixed-bed hydrogenation unit.The results showed that the nitrogen compounds mainly affected the initial activity of the catalyst,but had little effect on the stability of the catalyst.The PAHs had little effect on the initial activity of the catalyst,but could significantly accelerate the deactivation of the catalyst.Combined with the analysis of the reason of catalyst deactivation and the study of RTS technology,the direction of RTS technology process optimization was put forward,and the stability of catalyst was improved obviously after process optimization.展开更多
Thioetherification between mercaptan and diolefin is an efficient process to remove mercaptans in FCC gasoline at mild condition, during which the selective hydrogenation of diolefin to monoolefin is also expected. He...Thioetherification between mercaptan and diolefin is an efficient process to remove mercaptans in FCC gasoline at mild condition, during which the selective hydrogenation of diolefin to monoolefin is also expected. Here, Si O2 supported transition metal(Fe, Co, Ni, Mo and W) phosphides were tested for the thioetherification of isoprene and butanethiol on a fixed-bed reactor at 120℃ and 1.5 MPa H2, and their structure before and after reaction was characterized by means of XRD, HRTEM, N2 sorption, CO chemisorption, NH3-TPD, XPS and TG. It was found that, among different metal phosphides, Mo P/Si O2 showed the best performance, and the optimal nominal Mo P loading was 25%. Apart from the nature of metal, the density of metal and acid sites determined the catalyst performance. Metal site was mainly responsible for hydrogenation of isoprene, while acid site dominantly contributed to the thioetherification and the polymerization of olefins. Moreover, a balance between metallic and acidic functions is required to arrive at a desired performance. Excessive metal sites or acid sites led to the over-hydrogenation of isoprene or the severe polymerization of olefins, respectively. 25%Mo P/Si O2 was tested for 37 h time on stream, and butanethiol conversion maintained at 100%; although isoprene conversion remarkably decreased, the selectivity to isopentenes exceeded 80% after reaction for 11 h. We suggest that the deactivation of Mo P/Si O2 is mainly ascribed to the butanethiol poisoning and the carbonaceous deposit, especially the former.展开更多
A reliable kinetic model to describe the effects of various factors on the reaction rate and selectivity of pinene isomerization is developed. Furthermore, computational fluid dynamics(CFD) is applied to simulate the ...A reliable kinetic model to describe the effects of various factors on the reaction rate and selectivity of pinene isomerization is developed. Furthermore, computational fluid dynamics(CFD) is applied to simulate the solid–liquid dispersion in reactor. The catalyst Ti M is obtained by improving the composition and structure of hydrated titanium dioxide. The kinetic equation of pinene isomerization is deduced based on reaction mechanism and catalyst deactivation model. The kinetic equation of pinene isomerization reaction is fitted, and the results show that the fitted equation is correlated with the experimental data. The rate and selectivity of pinene isomerization reaction are affected by the amount of catalyst, deactivation of catalyst, structure of catalyst, reaction temperature and water content of catalyst. The solid–liquid distribution of the reactor is calculated by computational fluid dynamics numerical simulation, and the solid–liquid dispersion in commercial scale reactor is more uniform than that in lab-scale reactor.展开更多
Formic acid decomposition(FAD)is considered a promising hydrogen production route to facilitate the ambient storage and on demand release of hydrogen energy.To optimize the catalysts for FAD,efforts have been paid to ...Formic acid decomposition(FAD)is considered a promising hydrogen production route to facilitate the ambient storage and on demand release of hydrogen energy.To optimize the catalysts for FAD,efforts have been paid to explore the underlying reason for the varied catalytic activity among catalysts with similar composition but differed structure.However,such endeavors are highly challenging due to the deeply intermingled effects of electronic structure,particle size,and facets,etc.Herein,to separately evaluate the respective effects of these factors,a series of catalysts with the same surface electronic structure and different particle size was prepared by cation dipole adjustment method.The performance and characterization results showed that the catalysts with different sizes and facets exhibited similar intrinsic activity with deviation of less than 5%.However,they showed 252%deviation of site stability,indicating that only the optimized electronic structure could enhance the intrinsic activity and a smaller particle size could extend the catalyst’s life.展开更多
基金financial supported by the National Natural Science Foundation of China (22078065)Key Program of Qingyuan Innovation Laboratory (00221001)Quanzhou City Science & Technology Program of China (2020C008R)。
文摘Catalytic epoxidation of alkenes is an important type of organic reaction in chemical industry,and the deep insight into catalyst deactivation will help to develop new epoxidation process.In this work,series of quaternary ammoniums bearing different cationic sizes,i.e.MTOA+(methyltrioctylammonium,[(C_(8)H_(17))_(3)CH_(3)N]+),HTMA+(hexadecyltrimethylammonium,[(C_(16)H_(33))(CH_(3))_(3)N]+) and DMDOA+(dimethyldioctadecylammonium,[(C_(18)H_(37))_(2)(CH_(3))_(2)N]+) were incorporated with polyoxometalate (POM) anions to prepare phase transfer catalysts (PTCs),which were used in the styrene epoxidations.Among them,(MTOA)_(3)PW_(4)O_(24)exhibits the best catalytic performance judged from the highest styrene conversion rate(52%) and styrene oxide selectivity (93%),during which the styrene epoxidation conditions were optimized.Meanwhile,the deactivation mechanism of this kind of PTCs was proposed firstly,i.e.in the case of low H_(2)O_(2) content,the oxidant can only be used in the styrene epoxidation,in which the catalyst can transform into stable Keggin-type POM.But when the content of H_(2)O_(2) is higher,the excess H_(2)O_(2) can reactivate the Keggin-type POM into active (PW_(4)O_(24))_(3)-anions,which can trigger the ring-opening polymerization of styrene oxide.Consequently,the catalyst is deactivated by adhered poly(styrene oxide)irreversibly,which was determined by NMR spectra.In this situation,the active moiety{PO_(4)[WO(O_(2))_(2)]_(4)}_(3)-in phase-transfer catalytic system can break into some unidentified species with low W/P ratio with the presence of epoxides.This work will be beneficial for the design of new PTCs in alkene epoxidation in fine chemical industry.
基金We acknowledge financial support from National Engineering Research Center for Petroleum Refining Technology and Catalyst(RIPP,SINOPEC,Grant No.33600000-20-ZC0607-0009).
文摘How catalyst shape affects its deactivation is a crucial issue for quickly decaying catalysts such as zeolite in 2-butene and isobutane alkylation.In this work,steady simulations are used to determine the temperature and species distribution in fixed beds filled with particles of four shapes.Subsequently,unsteady simulations are used to study the deactivation behavior of the catalysts based on the steady simulation results.We describe the deactivation rate and type of catalyst deactivation by defining a local internal diffusivity,which is affected by catalytic activity.The results reveal that the internal diffusion distance of the catalyst determines the deactivation rate,whereas the local internal diffusivity determines its deactivation type.
文摘The kinetics of propane dehydrogenation and catalyst deactivation over Pt-Sn/Al2O3 catalyst were studied.Performance test runs were carried out in a fixed-bed integral reactor.Using a power-law rate expression for the surface reaction kinetics and independent law for deactivation kinetics,the experimental data were analyzed both by integral and a novel differential method of analysis and the results were compared.To avoid fluctuation of time-derivatives of conversion required for differential analysis,the conversion-time data were first fitted with appropriate functions.While the time-zero and rate constant of reaction were largely insensitive to the function employed,the rate constant of deactivation was much more sensitive to the function form.The advantage of the proposed differential method,however,is that the integration of the rate expression is not necessary which otherwise could be complicated or impossible.It was also found that the reaction is not limited by external and internal mass transfer limitations,implying that the employed kinetics could be considered as intrinsic ones.
基金the financial support from the Sinopec Catalyst Co.Ltd.,China。
文摘A series of model catalysts were obtained by treating commercial fresh and spent catalysts unloaded from the factory with different methods, including green oil dipping, extraction and high-temperature regeneration;finally, the deactivation behavior of the commercial catalyst for acetylene hydrogenation were studied. The influence of various possible deactivation factors on the catalytic performance was elucidated via detailed structural characterization, surface composition analysis, and activity evaluation.The results showed that green oil, carbon deposit and sintering of active metal were the main reasons for deactivation, among which green oil and carbon deposit led to rapid deactivation, while the activity could be recovered after regeneration by high-temperature calcination. The sintering of active metal components was attributed to the high-temperature regeneration in hydrothermal conditions, which was slow but irreversible and accounted for permanent deactivation. Thus, optimizing the regeneration is expected to extend the service life of the commercial catalyst.
基金funded by the National Research Council of Thailand (NRCT)the Second Century Foundation (C2F),Chulalongkorn University,ThailandResearcher Supporting Project RSP2024RR400,King Saud University,Saudi Arabia
文摘The selective aqueous-phase glycerol hydrogenolysis is a promising reaction to produce commercially useful 1,3-propanediol(1,3-PDO).The Pt-WOx bifunctional catalyst can catalyse the glycerol hydrogenol-ysis but the catalyst deactivation via sintering,metal leaching,and coking can predominantly occur in the aqueous phase reaction.In this work,the effect of reaction temperature,pressure and second promoter(Cu,Fe,Rh,Mn,Re,Ru,Ir,Sn,B,and P)on catalytic performance and deactivation behaviour of Pt/WOx/-Al2O3 was investigated.When doped with Rh,Mn,Re,Ru,Ir,B,and P,the second promoter boosts catalytic activity by promoting great dispersion of Pt on support and increasing Pt surface area.The increased Bronsted acid sites lead to selective synthesis of 1,3-PDO than 1,2-propanediol(1,2-PDO).The characterization studies of fresh and spent catalysts reveal that the main cause of catalyst deactivation is the Pt sintering,as interpreted based on XRD,CO chemisorption,and TEM analyses.The Pt sintering is affected depending on the second promoter that can either or reduce the interaction between Pt,WO_(χ)/γ and Al_(2)O_(3).As an electron acceptor of Pt in Pt/WO_(χ)/γ-Al_(2)O_(3),Re and Mn as second promoters resulted in increased Pt^(2+) on the catalytic surface,which strengthens the contact between Pt andγ-Al_(2)O_(3) and WO_(χ),resulting in a decrease in Pt sintering.The metal leaching and coking are not affected by the presence of second promoter.The catalyst modified with a second promoter possesses improved catalytic activity and 1,3-PDO production,however the stability continues to remain a challenge.The present work unrav-elled the determining parameters of catalytic activity and deactivation,thus providing a promising pro-tocol toward effective catalysts for glycerol hydrogenolysis.
基金supported by the National Natural Science Foundation of China(22008212,22078292,21902124)Natural Science Basic Research Planning Shaanxi Province of China(2017ZDJC-29)+2 种基金Key Research and Development Project of Shaanxi Province(2018ZDXM-GY-173)China Postdoctoral Science Foundation(2019 M663848)Open cooperative innovation fund of Xi'an Institute of modern chemistry(SYJJ48).
文摘Chlorotrifluoroethylene(CTFE)is a vital fluorinated olefinic monomer produced through the catalytic hydrodechlorination of trichlorotrifluoroethane(CFC-113),an eco-friendly process.However,hydrodechlorination catalysts for olefin production often suffer from poor stability.The Pd/AC catalyst and Pd-Cu/AC catalyst prepared by co-impregnation method exhibited poor stability,Pd-Cu/AC catalyst with CFC-113 conversion dropping to around 37%after 50 h of hydrodechlorination reaction.Brunauer-Emmett-Teller,transmission electron microscopy,X-ray photoelectron spectroscopy,and X-ray diffraction of fresh and deactivated Pd/AC catalysts indicate that the deactivation of Pd/AC catalysts is due to high-temperature agglomeration of Pd.Comparative analysis of fresh and deactivated Pd-Cu/AC catalysts using Brunauer-Emmett-Teller,transmission electron microscopy,and thermogravimetric analysis techniques revealed decreased dispersion of active sites,reduced surface area,catalyst aggregation deactivation,and a significant decrease in Cu content.Furthermore,the results of NH3-TPD revealed that the acid sites of the catalyst increased significantly.X-ray diffraction spectra indicated the formation of new species,basic copper chloride(Cu_(2)(OH)_(3)Cl),during the reaction.As the reaction progressed,these new species agglomerated,leading to a gradual loss of catalyst activity.Moreover,the deactivated catalyst was successfully reactivated using a simple alkaline washing method.
基金Supports by the National Key Research and Development Plan(2016YFB0301503)the Jiangsu Natural Science Foundation for Distinguished Young Scholars(BK20150044)+3 种基金the National Natural Science Foundation of China(91534110,21606124)the Natural Science Foundation of the Higher Education Institutions of Jiangsu Province(14KJB530004)the Foundation from State Key Laboratory of Materials-Oriented Chemical Engineering(ZK201402,ZK201407)the Technology Innovation Foundation for Science and Technology Enterprises in Jiangsu Province(BC2015008)
文摘The alkylation of benzene with isopropanol over beta-zeolite is a more cost-effective solution to cumene production. During the benzene alkylation cycles, the cumene selectivity slowly increased, while the benzene conversion presented the sharp decrease due to catalyst deactivation. The deactivation mechanism of betazeolite catalyst was investigated by characterizing the fresh and used catalysts. The XRD, SEM and TEM results show that the crystalline and particle size of the beta-zeolite catalyst almost remained stable during the alkylation cycles. The drop in catalytic activity and benzene conversion could be explained by the TG, BET,NH_3-TPD and GC–MS results. The organic matters mainly consisted of ethylbenzene, p-xylene and 1-ethyl-3-(1-methyl) benzene produced in the benzene alkylation deposited in the catalyst, which strongly reduced the specific surface area of beta-zeolite catalyst. Moreover, during the reaction cycles, the amount of acidity also significantly decreased. As a result, the catalyst deactivation occurred. To maintain the catalytic performance,the catalyst regeneration was carried out by using ethanol rinse and calcination. The deactivated catalyst could be effectively regenerated by the calcination method and the good catalytic performance was obtained.
文摘A physical mixture of alkali-promoted iron catalyst with binder based on Fischer-Tropsch synthesis and an acidic co-catalyst (HZSM5) for syngas conversion to hydrocarbons was studied in a fixed bed micro reactor. Deactivation data were obtained during the synthesis over a 1400 h period. The deactivation studies on iron catalyst showed that this trend followed the phase transformation Fe2.2C ( ε′) → Fe5C2 (χ) → Fe3C (θ), and the final predominant phase of the catalyst was Fe3C (θ). Deactivation of zeolite component in bifunctional catalyst may be caused by coking over the zeolitic component, dealumination of zeolite crystals, and migration of alkali promoters from iron catalyst under synthesis conditions. The deactivation rate of iron catalyst was also obtained.
文摘A nano-structured iron catalyst for syngas conversion to hydrocarbons in Fischer-Tropsch synthesis(FTS) was prepared by micro-emulsion method.Compositions of bulk iron phase and phase transformations of carbonaceous species during catalyst deactivation in FTS reaction were characterized by temperature-programmed surface reaction with hydrogen(TPSR-H 2 ),and XRD techniques.Many carbonaceous species on surface and bulk of the nano-structured iron catalysts were completely identified by combined TPSR-H 2 and XRD spectra and which were compared with those recorded on conventional co-precipitated iron catalyst.The results reveal that the catalyst deactivation results from the formation of inactive carbide phases and surface carbonaceous species like graphite,and it will be increased when the particle size of iron oxides was reduced in FTS iron catalyst.
基金supported by the Natural Science Foundation of China (21306046)the Open Project of State Key Laboratory of Chemical Engineering (SKL-Che-15C03)+2 种基金the Fundamental Research Funds for the Central Universities (WA1514013)the 111 Project of Ministry of Education of China (B08021)supported by the China Scholarship Council (CSC) for the research at Norwegian University of Science and Technology (NTNU)
基金supported by the Cultivation Project of Major Achievements Transformation of Sichuan Provincial Education Department(#14CZ0005)supported by the Natural Science Foundation of China(#21406184)
基金supported by the Smart Mix Program of the Netherlands Ministry of Economic Affairs and the Netherlands Ministry of Education, Culture and Science
文摘Nickel, cobalt, copper and platinum nanoparticles supported on carbon nano-fibers were evaluated with respect to their stability, catalytic activity and selectivity in the aqueous phase reforming of ethylene glycol (230 ℃, autogenous pressure, batch reactor). The initial surface-specific activities for ethylene glycol reforming were in a similar range but decreased in the order of Pt (15.5 h-1 ) 〉Co(13.0 h 1 ) 〉Ni(5.2 h-1) while the Cu catalyst only showed low dehydrogenation activity. The hydrogen molar selectivity decreased in the order of Pt (53%)〉Co(21%)〉Ni (15%) as a result of the production of methane over the latter two catalysts. Over the Co catalyst acids were formed in the liquid phase while alcohols were formed over Ni and Pt. Due to the low pH of the reaction mixture, especially in the case of Co (as a result of the formed acids), significant cobalt leaching occurs which resulted in a rapid deactivation of this catalyst. Investigations of the spent catalysts with various techniques showed that metal particle growth is responsible for the deactivation of the Pt and Ni catalysts. In addition, coking might also contribute to the deactivation of the Ni catalyst.
基金financially supported by the Hydrogenation Process and Hydrogenation Catalyst Laboratory (RIPP,SINOPEC)
文摘The effect of polycyclic aromatic hydrocarbons(PAHs)on the stability of the hydrogenation catalyst for production of ultra-low sulfur diesel was studied in a pilot plant using Ni-Mo-W/γ-Al_(2)O_(3)catalyst.The mechanisms of catalyst deactivation were analyzed by the methods of elemental analysis,nitrogen adsorption-desorption,thermogravimetry-mass spectrometry(TG-MS)technology,X-ray photoelectron spectroscopy(XPS)and high resolution transmission electron microscopy(HRTEM).The results demonstrated that PAHs had little effect on the activity of catalyst at the beginning of operation,during which the reaction temperature was increased by only 1-4℃.However,the existence of PAHs significantly accelerated the deactivation of catalyst and weakened the stability of catalyst.This phenomenon could be explained by the reason that the catalyst deactivation is not only related to the formation of carbon deposit,but is also closely related to the loss of pore volume and the decrease of Ni-W-S phase ratio after adding PAHs.
基金supported by the Research and Technology Directorate of National Iranian Oil Company
文摘Cobalt supported on carbon nanotubes (CNTs)-covered alumina has been recently developed and successfully utilized as a catalyst in Fischer-Tropsch synthesis (FTS). Problems associated with shaping of Co/CNTs into extrudates or pellets as well as catalyst attrition rendered these materials unfavorable for industrial applications. In this investigation regular γ- and nano-structured (N-S) alumina as well as CNTs-covered regular γ- and N-S-alumina supports were impregnated by cobalt nitrate solution to make new cobalt-based catalysts which were also promoted by Ru. The catalysts were characterized and tested in a micro reactor to evaluate their applicability in FTS. γ-Al2O3 was prepared by calcination of bohemite and N-S-Al2O3 was prepared by sol-gel method using aluminum chloride as starting material. Catalyst evaluations indicated that N-S-Al2O3 was superior to regular γ-Al2O3 and that CNTs-covered alumina supports were favored over non-covered ones in terms of activity and heavy hydrocarbon selectivity. These were justified by porosimetric characteristics of the catalysts and existence of CNTs points of view. CNTs-covered catalysts also showed higher wax selectivity and better resistance to deactivation. Furthermore, TPR analysis indicated that the cobalt aluminate phase, which is responsible for the permanent deactivation of alumina supported Co-based catalysts, did not form on alumina supported Co-based catalysts covered with CNTs due to weaker interactions between cobalt and alumina.
基金financial support from the National Natural Science Foundation of China(21991092,21991090,22022202,21972142,21902153,21974138)the Chinese Academy of Sciences(QYZDY-SSW-SC024)the Dalian Institute of Chemical Physics(DICP I201926,DICP I201947)。
文摘Low-carbon process for resource utilization of polycyclic aromatic hydrocarbons(PAHs)in zeolitecatalyzed processes,geared to carbon neutrality-a prominent trend throughout human activities,has been bottlenecked by the lack of a complete mechanistic understanding of coking and decoking chemistry,involving the speciation and molecular evolution of PAHs,the plethora of which causes catalyst deactivation and forces regeneration,rendering significant CO_(2) emission.Herein,by exploiting the high-resolution matrix-assisted laser desorption/ionization Fourier-transform ion cyclotron resonance mass spectrometry(MALDI FT-ICR MS),we unveil the missing fingerprints of the mechanistic pathways for both formation and decomposition of cross-linked cage-passing PAHs for SAPO-34-catalyzed,industrially relevant methanol-to-olefins(MTO)as a model reaction.Notable is the molecule-resolved symmetrical signature:their speciation originates exclusively from the direct coupling of in-cage hydrocarbon pool(HCP)species,whereas water-promoted decomposition of cage-passing PAHs initiates with selective cracking of inter-cage local structures at 8-rings followed by deep aromatic steam reforming.Molecular deciphering the reversibly dynamic evolution trajectory(fate)of full-spectrum aromatic hydrocarbons and fulfilling the real-time quantitative carbon resource footprints advance the fundamental knowledge of deactivation and regeneration phenomena(decay and recovery motifs of autocatalysis)and disclose the underlying mechanisms of especially the chemistry of coking and decoking in zeolite catalysis.The positive yet divergent roles of water in these two processes are disentangled.These unprecedented insights ultimately lead us to a steam regeneration strategy with valuable CO and H_(2) as main products,negligible CO_(2) emission in steam reforming and full catalyst activity recovery,which further proves feasible in other important chemical processes,promising to be a sustainable and potent approach that contributes to carbon-neutral chemical industry.
基金The authors are grateful for the financial support of The Sate Key Fundamental Research Project and the Natural Science Foundation of China.
文摘Dehydrogenation of ethylbenzene (EB) to styrene (ST) in the presence of CO2, in which EB dehydrogenation is coupled with the reverse water-gas shift (RWGS), was investigated extensively through both theoretical analysis and experimental characterization. The reaction coupling proved to be superior to the single dehydrogenation in several respects. Thermodynamic analysis suggests that equilibrium conversion of EB can be improved greatly by reaction coupling due to the simultaneous elimination of the hydrogen produced from dehydrogenation. Catalytic tests proved that iron and vanadium supported on activated carbon or Al2O3 with certain promoters are potential catalysts for this coupling process. The catalysts of iron and vanadium are different in the reaction mechanism, although ST yield is always associated with CO2 conversion over various catalysts. The two-step pathway plays an important role in the coupling process over Fe/Al2O3, while the one-step pathway dominates the reaction over V/Al2O3. Coke deposition and deep reduction of active components are the major causes of catalyst deactivation. CO2 can alleviate the catalyst deactivation effectively through preserving the active species at high valence in the coupling process, though it can not suppress the coke deposition.
基金This work was financially supported by the Technology Development Project of SINOPEC(121025)All of the staff in our laboratory had provided a lot of support in the analysis of oil samples and catalyst characterization.
文摘The RTS technology can produce ultra-low sulfur diesel at lower costs using available hydrogenation catalyst and device.However,with the increase of the mixing proportion of secondary processed diesel fuel in the feed,the content of nitrogen compounds and polycyclic aromatic hydrocarbons in the feed increased,leading to the acceleration of the deactivation rate of the primary catalyst and the shortening of the service cycle.In order to fully understand the reason of catalyst deactivation,the effect of mixing secondary processed diesel fuel oil on the operating stability of the catalyst in the first reactor was investigated in a medium-sized fixed-bed hydrogenation unit.The results showed that the nitrogen compounds mainly affected the initial activity of the catalyst,but had little effect on the stability of the catalyst.The PAHs had little effect on the initial activity of the catalyst,but could significantly accelerate the deactivation of the catalyst.Combined with the analysis of the reason of catalyst deactivation and the study of RTS technology,the direction of RTS technology process optimization was put forward,and the stability of catalyst was improved obviously after process optimization.
基金supported by the State Key Laboratory of Catalytic Materials and Reaction Engineering(RIPP,SINOPEC)
文摘Thioetherification between mercaptan and diolefin is an efficient process to remove mercaptans in FCC gasoline at mild condition, during which the selective hydrogenation of diolefin to monoolefin is also expected. Here, Si O2 supported transition metal(Fe, Co, Ni, Mo and W) phosphides were tested for the thioetherification of isoprene and butanethiol on a fixed-bed reactor at 120℃ and 1.5 MPa H2, and their structure before and after reaction was characterized by means of XRD, HRTEM, N2 sorption, CO chemisorption, NH3-TPD, XPS and TG. It was found that, among different metal phosphides, Mo P/Si O2 showed the best performance, and the optimal nominal Mo P loading was 25%. Apart from the nature of metal, the density of metal and acid sites determined the catalyst performance. Metal site was mainly responsible for hydrogenation of isoprene, while acid site dominantly contributed to the thioetherification and the polymerization of olefins. Moreover, a balance between metallic and acidic functions is required to arrive at a desired performance. Excessive metal sites or acid sites led to the over-hydrogenation of isoprene or the severe polymerization of olefins, respectively. 25%Mo P/Si O2 was tested for 37 h time on stream, and butanethiol conversion maintained at 100%; although isoprene conversion remarkably decreased, the selectivity to isopentenes exceeded 80% after reaction for 11 h. We suggest that the deactivation of Mo P/Si O2 is mainly ascribed to the butanethiol poisoning and the carbonaceous deposit, especially the former.
基金the National Ministry of Science and Technology of China(No.2017YFB0602401)the National Natural Science Foundation of China(No.21776173 and 21625603)+2 种基金the Program of Shanghai Subject Chief Scientist(No.18XD1402000)the Fujian Green Pine Co.,Ltd.the computational support from the Center for High Performance Computing,Shanghai Jiao Tong University for supporting this work。
文摘A reliable kinetic model to describe the effects of various factors on the reaction rate and selectivity of pinene isomerization is developed. Furthermore, computational fluid dynamics(CFD) is applied to simulate the solid–liquid dispersion in reactor. The catalyst Ti M is obtained by improving the composition and structure of hydrated titanium dioxide. The kinetic equation of pinene isomerization is deduced based on reaction mechanism and catalyst deactivation model. The kinetic equation of pinene isomerization reaction is fitted, and the results show that the fitted equation is correlated with the experimental data. The rate and selectivity of pinene isomerization reaction are affected by the amount of catalyst, deactivation of catalyst, structure of catalyst, reaction temperature and water content of catalyst. The solid–liquid distribution of the reactor is calculated by computational fluid dynamics numerical simulation, and the solid–liquid dispersion in commercial scale reactor is more uniform than that in lab-scale reactor.
基金supported by the National Natural Science Foundation of China(No.21733004)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDA21090400)the Natural Science Foundation of Jilin Province(Nos.20190201300JC,20200201001JC)。
文摘Formic acid decomposition(FAD)is considered a promising hydrogen production route to facilitate the ambient storage and on demand release of hydrogen energy.To optimize the catalysts for FAD,efforts have been paid to explore the underlying reason for the varied catalytic activity among catalysts with similar composition but differed structure.However,such endeavors are highly challenging due to the deeply intermingled effects of electronic structure,particle size,and facets,etc.Herein,to separately evaluate the respective effects of these factors,a series of catalysts with the same surface electronic structure and different particle size was prepared by cation dipole adjustment method.The performance and characterization results showed that the catalysts with different sizes and facets exhibited similar intrinsic activity with deviation of less than 5%.However,they showed 252%deviation of site stability,indicating that only the optimized electronic structure could enhance the intrinsic activity and a smaller particle size could extend the catalyst’s life.