Styrene epoxidation catalyzed by polyoxometalate/quaternary ammonium phase transfer catalysts: The effect of cation size and catalyst deactivation mechanism

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.

Effect of Particle Shape on Catalyst Deactivation during 2-Butene and Isobutane Alkylation of Liquid Phase in Fixed-Bed Reactor Using Particle-Resolved CFD Simulation

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.

Studies on Catalyst Deactivation Rate and Byproducts Yield during Conversion of Methanol to Olefins

The conversion of methanol to olefins (MTO) over the SAPO-34 catalyst in fixed-bed microreactor was studied. The effect of reaction temperatures for methanol conversion to olefins and byproducts was investigated. A temperature of 425 ℃ appeared to be the optimum one suitable for conversion of methanol to olefins. Since the presence of water could increase the olefins selectivity, the methanol conversion reactions with mixed water/methanol feed were also studied. The effect of weight hourly space velocity on conversion of methanol was also studied. The results indicated that the olefins selectivity was significantly increased as WHSV increased till approximately 7.69 h-1 then it began to level off. Different factors affecting the catalyst deactivation rate was studied, showing that the catalyst deactivation time was dependent on reaction conditions, and temperatures higher and lower than the optimal one made the catalyst deactivation faster. Adding water to methanol could slow down the catalyst deactivation rate.

Kinetic study of propane dehydrogenation and catalyst deactivation over Pt-Sn/Al_2O_3catalyst

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.

Towards the insights into the deactivation behavior of acetylene hydrogenation catalyst

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.

Understanding the catalytic performance and deactivation behaviour of second-promoter doped Pt/WO_(χ)/γ-Al_(2)O_(3) catalysts in the glycerol hydrogenolysis for selective and cleaner production of 1,3-propanediol

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.

Hydrodechlorination of trifluoro-trichloroethane to chlorotrifluoroethylene:Revealing the deactivation mechanism and regeneration strategy of Pd-Cu/AC 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.

Deactivation mechanism of beta-zeolite catalyst for synthesis of cumene by benzene alkylation with isopropanol

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.

The effect of cations(NH_4^+,Na^+,K^+,and Ca^(2+)) on chemical deactivation of commercial SCR catalyst by bromides

Alkali and alkaline‐earth metals from fly ash have a significant deactivation effect on catalysts used for selective catalytic reduction of NOx by NH3(NH3‐SCR).Bromides are considered effective additives to improve Hg0 oxidation on SCR catalysts.In this work,the effects of different bromides(NH4Br,NaBr,KBr,and CaBr2)on a commercial V2O5‐WO3/TiO2 catalyst were studied.NOx conversion decreased significantly over the KBr‐poisoned catalyst(denoted as L‐KBr),while that over NaBr‐and CaBr2‐poisoned catalysts(denoted as L‐NaBr and L‐CaBr,respectivity)decreased to a lesser extent compared with the fresh sample.Poor N2 selectivity was observed over L‐NaBr,L‐KBr and L‐CaBr catalysts.The decrease in the ratio of chemisorbed oxygen to total surface oxygen(Oα/(Oα+Oβ+Ow)),reducibility and surface acidity might contribute to the poor activity and N2 selectivity over L‐KBr catalyst.The increased Oαratio was conducive to the enhanced reducibility of L‐CaBr.Combined with enhanced surface acidity,this might offset the negative effect of the loss of active sites by CaBr2 covering.The overoxidation of NH3 and poor N2 selectivity in NH3 oxidation should retard the SCR activity at high temperatures over L‐CaBr catalyst.The increased basicity might contribute to increased NOx adsorption on L‐KBr and L‐CaBr catalysts.A correlation between the acid‐basic and redox properties of bromide‐poisoned catalysts and their catalytic properties is established.

Deactivation studies of bifunctional Fe-HZSM5 catalyst in Fischer-Tropsch process

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.

Deactivation studies of nano-structured iron catalyst in Fischer-Tropsch synthesis

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.

Iron-based Fischer–Tropsch synthesis of lower olefins: The nature of χ-Fe_5C_2 catalyst and why and how to introduce promoters

As a sustainable and short-flow process, iron-catalyzed direct conversion of CO-rich syngas to lower olefins without intermediate steps, i.e., Fischer–Tropsch-to-Olefins (FTO), has received increasing attention. However, its fundamental understanding is usually limited by the complex crystal phase composition in addition to the interferences of the promoter effects and inevitable catalyst deactivation. Until recently, the combination of multiple in-situ/ex-situ characterizations and theoretical studies has evidenced Hägg iron carbide (χ-Fe5C2) as the dominant active phase of iron-based Fischer–Tropsch catalysts. This perspective attempts to review and discuss some recent progresses on the nature of χ-Fe5C2catalyst and the crucial effects of promoters on the FTO performance from theoretical and experimental viewpoints, aiming to provide new insights into the rational design of iron-based FTO catalysts. © 2016 Science Press

Catalytic performances of Ni/mesoporous SiO_2 catalysts for dry reforming of methane to hydrogen

Several mesoporous silicas with different morphologies were controllably prepared by sol-gel method with adjustable ratio of dual template, and they were further impregnated with aqueous solution of nickel nitrate, followed by calcination in air. The synthesized silica supports and supported nickel samples were characterized using N2-adsorption/desorption, X-ray diffraction (XRD), H2temperature-programmed reduction (H2-TPR), Scanning electron microscope (SEM), Transmission electron microscope (TEM) and thermo-gravimetric analysis (TGA-DTG) techniques. The Ni nanoparticles supported on shell-like silica are highly dispersed and yielded much narrower nickel particle-size than those on other mesoporous silica. The methane reforming with dioxide carbon reaction results showed that Ni nanoparticles supported on shell-like silica carrier exhibited the better catalytic performance and catalytic stability than those of nickel catalyst supported on other silica carrier. The thermo-gravimetric analysis on used nickel catalysts uncovered that catalyst deactivation depends on the type and nature of the coke deposited. The heterogeneous nature of the deposited coke was observed on nickel nanoparticles supported on spherical and peanut-like silica. Much narrower and lower TGA derivative peak was founded on Ni catalyst supported on the shell-like silica. © 2016 Science Press

Stability and activity of carbon nanofiber-supported catalysts 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.

Effect of Polycyclic Aromatic Hydrocarbons on the Stability of Hydrogenation Catalyst for Producing Ultra-Low Sulfur Diesel

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.

Cobalt supported on CNTs-covered γ-and nano-structured alumina catalysts utilized for wax selective Fischer-Tropsch synthesis

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.

Catalytic behavior in propane aromatization using GA-MFI catalyst

Ga-Al-MFI samples were synthesized in hydrothermal conditions from gels of composition 1.08CH3NH2- 0.134TPABr-1SiO2-xAl2O3-yGa2O3-40H2O at 175 ℃ for 7 days, with x = 0.005 and 0.0025, y = 0.005, 0,010 and 0.020. The samples were characterized by XRD, BET measurements, thermal analysis （TGA-DTA） atomic absorption and high resolution solid state MAS 27Al and 71Ga NMR measurements. The aromatization of propane was studied as catalytic test. The activity and selectivity of the catalysts were determined for benzene, toluene and xylenes on the one hand and for methane and ethane on the other hand. The most active sample was obtained with the highest Ga/AI ratio. For this sample, the BTX selectivity obtained by aromatization was always higher than the hydrocracking selectivity leading to methane and ethane. The relative amount of toluene was higher than that of benzene and ofxylenes. The samples were deactivated by coke formation that was revealed more severe for the most active sample,

Surface chemical characterization of deactivated low-level mercury catalysts for acetylene hydrochlorination

Mercury-containing catalysts are widely used for acetylene hydrochlorination in China. Surface chemical characteristics of the fresh low-level mercury catalysts and spent low-level mercury catalysts were compared using multiple characterization methods. Pore blockage and active site coverage caused by chlorine-containing organics are responsible for catalyst deactivation. The reactions of chloroethylene and acetylene with chlorine free radical can generate chlorine-containing organic species. SiO_2 and functional groups on activated carbon contribute to the generation of carbon deposition. No significant reduction in the total content of mercury was observed after catalyst deactivation, while there was mercury loss locally. The irreversible loss of HgCl_2 caused by volatilization, reduction and poisoning of elements S and P also can lead to catalyst deactivation. Si, Al, Ca and Fe oxides are scattered on the activated carbon. Active components are still uniformly absorbed on activated carbon after catalyst deactivation.

Coking and decoking chemistry for resource utilization of polycyclic aromatic hydrocarbons(PAHs)and low-carbon process

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.

Theoretical and Experimental Study on Reaction Coupling: Dehydrogenation of Ethylbenzene in the Presence of Carbon Dioxide

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.