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.

Deactivation mechanism for water splitting:Recent advances

Hydrogen(H_(2)) has been regarded as a promising alternative to fossil-fuel energy.Green H_(2) produced via water electrolysis(WE)powered by renewable energy could achieve a zero-carbon footprint.Considerable attention has been focused on developing highly active catalysts to facilitate the reaction kinetics and improve the energy efficiency of WE.However,the stability of the electrocatalysts hampers the commercial viability of WE.Few studies have elucidated the origin of catalyst degradation.In this review,we first discuss the WE mechanism,including anodic oxygen evolution reaction(OER)and cathodic hydrogen evolution reaction(HER).Then,we provide strategies used to enhance the stability of electrocatalysts.After that,the deactivation mechanisms of the typical commercialized HER and OER catalysts,including Pt,Ni,RuO_(2),and IrO_(2),are summarized.Finally,the influence of fluctuating energy on catalyst degradation is highlighted and in situ characterization methodologies for understanding the dynamic deactivation processes are described.

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 acetone to isobutene conversion over Y/Beta catalyst

The conversion of acetone derived from biomass to isobutene has attracted extensive attentions.In comparison with Brønsted acidic catalyst,Lewis acidic catalyst could exhibit a better catalytic performance with a higher isobutene selectivity.However,the catalyst stability remains a key problem for the long-running acetone conversion and the reasons for catalyst deactivation are poorly understood up to now.Herein,the deactivation mechanism of Lewis acidic Y/Beta catalyst during the acetone to isobutene conversion was investigated by various characterization techniques,including acetone-temperature-programmed surface reaction,gas chromatography-mass spectrometry,in situ ultraviolet-visible,and ^(13)C cross polarization magic angle spinning nuclear magnetic resonance spectroscopy.A successive aldol condensation and cyclization were observed as the main side-reactions during the acetone conversion at Lewis acidic Y sites.In comparison with the low reaction temperature,a rapid formation and accumulation of the larger cyclic unsaturated aldehydes/ketones and aromatics could be observed,and which could strongly adsorb on the Lewis acidic sites,and thus cause the catalyst deactivation eventually.After a simple calcination,the coke deposits could be easily removed and the catalytic activity could be well restored.

A critical review towards the causes of the iron-based catalysts deactivation mechanisms in the selective oxidation of hydrogen sulfide to elemental sulfur from biogas

Hydrogen sulfide(H_(2)S) not only presents significant environmental concerns but also induces severe corrosion in industrial equipment,even at low concentrations.Among various technologies,the selective oxidation of hydrogen sulfide(SOH_(2)S) to elemental sulfur(S) has emerged as a sustainable and environmentally friendly solution.Due to its unique properties,iron oxide has been extensively investigated as a catalyst for SOH_(2)S;however,rapid deactivation has remained a significant drawback.The causes of iron oxide-based catalysts deactivation mechanisms in SOH_(2)S,including sulfur or sulfate deposition,the transformation of iron species,sintering and excessive oxygen vacancy formation,and active site loss,are thoroughly examined in this review.By focusing on the deactivation mechanisms,this review aims to provide valuable insights into enhancing the stability and efficiency of iron-based catalysts for SOH_(2)S.

Deactivation mechanism of CaO in a flow type dimethyl carbonate synthesis process

It is well known that calcium oxide (CaO) has better catalytic efficiency than most heterogeneous catalysts in many transesterification reactions. However, the gradual deactivation problem prevents its large-scale application in industry. In this paper, the deactivation mechanism of CaO in a fixed-bed reactor is investigated based on the transesterification reaction of propylene carbonate and methanol. The leaching amount of CaO during the reaction was estimated by the concentration of Ca in the products. The pretreated and recovered catalysts were characterized by FT-IR, XRD, TG-MS and SEM-EDS. It is evident from experiments and characterization that the deactivation process of CaO is accompanied by the leaching of calcium species and the generation of CaCO3, which are also verified by DFT calculations. At high temperature and high weight hourly space velocity, the deactivation was attributed to the formation of dense CaCO3 shell, which prevents the contact between the feedstock and the active species inside.

Deactivation Kinetics of Nitrile Hydratase in Free Resting Cells

Nitrile hydratase (NHase) is an important industrial enzyme used for acrylamide production from acrylonitrile.The deactivation kinetics of NHases in free resting cells of Rhodococcus sp.was presented based on a bi-steady state assumption.Effects of hydration temperature,product concentration and substrate concentration on NHase deactivation were investigated experimentally and correlated with a first order deactivation kinetics.The results showed that the hydration temperature and product concentration were major factors governing the deactivation of NHases under substrate-feeding conditions.When acrylamide concentration was higher than 250 g·L1,the deactivation of NHases became serious and the bi-steady state assumption was not applicable.When the hydration temperature was controlled at a relatively higher level such as 28°C,the total deactivation rate constant was about 2.8-fold of that at 20°C.

MONTE-CARLOSIMULATION OF CATALYST DEACTIVATION

Catalyst deactivation due to coking is microscopically analyzed,then a model is presented,based upon the analogy between coke deposition and solid aggregation.The Monte Carlo simulation results show that the model can fit the experimental data in all cases.With this model,the mechanism of formation of coke with different shapes is derived and the relation between the catalytic activity and coke shape is theoretically demonstrated.In addition,the model described in this paper can also be used to simulate the catalyst preparation so as to make more useful and efficient catalysts.The model in this paper is very simple,with only two parameters that indicate the nature of catalyst deactivation.The extension of the model to more complicated systems is also discussed.

Stability and deactivation of OER electrocatalysts: A review

Recently, H_(2) has attracted increasing attention as green energy carrier holding the possibility to replace fossil fuel-based energy sources and thereby reduce CO_(2) emissions. Green hydrogen can be generated by water electrolysis using renewable energies like wind and solar power. When it is combusted, only water forms as by-product. However, the efficiency of water electrolysis is hampered by the anodic oxygen evolution reaction(OER) because of the slow kinetics which leads to a high overpotential. Therefore, many catalysts have been developed for OER to facilitate the kinetics and reduce the overpotential. In addition to electrocatalytic activity, the stability of the catalysts is imperative for industrial application and has been intensively studied. In this review, we cover recent findings on the stability and deactivation mechanisms of OER catalysts. We discuss the correlation between OER activity and stability, methodologies and experimental techniques to study the stability and deactivation as well as the deactivation mechanisms, together with factors influencing stability. Furthermore, strategies for stabilizing and regenerating OER catalysts as well as methods to predict stability are summarized. Finally, the review highlights emerging methodologies yet to be explored and future directions of stability studies and the design of highly stable OER catalysts.

Coking kinetics and influence of reaction-regeneration on acidity, activity and deactivation of Zn/HZSM-5 catalyst during methanol aromatization

The coking kinetics and reaction-regeneration on Zn/HZSM-5 （Zn/HZ） catalyst in the conversion of methanol to aromatics were investigated. The highest initial benzene, toluene and xylene （BTX） yield of ca. 67.7% was obtained on fresh Zn/HZ catalyst, which showed the worst catalytic stability. The cycle of reaction-regeneration significantly modified the texture and acidity of Zn/HZ catalyst, which in turn affected its catalytic performance and coking behavior in methanol conversion to BTX. The residual carbon located on the surface of Zn/HZ catalyst led to the decrease of acid sites and the change on the acid sites distribution, which played an important roles on its activity and deactivation. It was found that the high B/L ratio and the low total acid sites concentration of the Zn/HZ catalyst favored to the high BTX yield and good catalytic stability in methanol conversion.

Excavator Energy-saving Efficiency Based on Diesel Engine Cylinder Deactivation Technology

The hydraulic excavator energy-saving research mainly embodies the following three measures： to improve the performance of diesel engine and hydraulic component, to improve the hydraulic system, and to improve the power matching of diesel-hydraulic system-actuator. Although the above measures have certain energy-saving effect, but because the hydraulic excavator load changes frequently and fluctuates dramatically, so the diesel engine often works in high-speed and light load condition, and the fuel consumption is higher. Therefore, in order to improve the economy of diesel engine in light load, and reduce the fuel consumption of hydraulic excavator, energy management concept is proposed based on diesel engine cylinder deactivation technology. By comparing the universal characteristic under diesel normal and deactivated cylinder condition, the mechanism that fuel consumption can be reduced significantly by adopting cylinder deactivation technology under part of loads condition can be clarified. The simulation models for hydraulic system and diesel engine are established by using AMESim software, and fuel combustion consumption by using cylinder-deactivation-technology is studied through digital simulation approach. In this way, the zone of cylinder deactivation is specified. The testing system for the excavator with this technology is set up based on simulated results, and the results show that the diesel engine can still work at high efficiency with part of loads after adopting this technology; fuel consumption is dropped down to 11% and 13% under economic and heavy-load mode respectively under the condition of driving requirements. The research provides references to the energy-saving study of the hydraulic excavators.

O2（1△g） Deactivation on O2-adsorbed Metal Surfaces

A flow system was set up to measure the quenching probability ~ of O2（1△g） on various O2- adsorbed metal surfaces including Cu, Cr, Ni, and Ag. increased with both the duration of the experiment and the O2（1△g） concentration. After several hours evacuation to a few Pa, γ can return to its original value. A deactivation mechanism of O2（1△g） is suggested by considering first the weak chemisorption of O2（1△g） on the surface adsorption sites, followed by the near resonant energy transfer between the gas phase O2（1△g） and surface O2（1△g）. A phenomenological model in accord with the experimental fact has been proposed together with relevant kinetic equations.

Investigation of the characteristics and deactivation of catalytic active center of Cr-Al_2O_3 catalysts for isobutane dehydrogenation

Deactivation mechanism of Cr-Al2O3catalyst and the interaction of Cr-A1 in the dehydrogenation of isobutane, as well as the nature of the catalytic active center, were studied using XRD, SEM, XPS, H2-TPR, isobutane-TPR and TPO techniques. The results revealed that the deactivation of Cr-Al2O3 catalyst was mainly caused by carbon deposition on its surface. The Cr3＋ ion could not be reduced by hydrogen but could be reduced to Cr2＋ by hydrocarbons and monoxide carbon. The active center for isobutane dehydrogenation could be Cr2＋/Cr3＋ produced from Cr6＋ by the on line reduction of hydrocarbon and carbon monoxide. The binding energy of Al3＋ was strongly affected by the state of chromium cations in the catalysts.

Study on the deactivation and regeneration of the ZSM-5 catalyst used in methanol to olefins

ZSM-5 zeolite catalyst modified by a trace of metal cations shows high activity and high selectivity for the reaction of methanol to olefins （MTO）, but it inclines to deactivate during the reaction. In this paper, the mechanism of the catalyst deactivation and the regeneration method were studied by X-ray diffraction （XRD）, N2 adsorption-desorption, infrared spectra （IR）, and infrared spectra coupled with NH3 molecular probes （IR-NH3）. These characterizations indicated that coke formation was the main reason for the catalyst deactivation. To regenerate the deactivated catalyst, two methods, i.e., calcination and methanol leaching, were used. N2 adsorption-desorption, IR and IR-NH3 characteriza-tions showed that both methods can eliminate coke deposited on the catalyst and make the catalyst reactivated. XRD showed that the structure of the catalyst did not change after regeneration. Interestingly, the regenerated catalyst even showed better catalytic performance of the MTO reaction than the fresh one. Besides, the calcination regeneration can eliminate coke more completely, however, the methanol leaching method can be more easily carried out in situ in the reactor.

Understanding the deactivation behavior of Pt/WO3/Al2O3 catalyst in the glycerol hydrogenolysis reaction

The selective hydrogenolysis of glycerol to 1,3-propanediol is a highly important reaction for both improving the profitability of biodiesel and valorization of biomass.While intensive research efforts have been devoted to enhancing the catalytic activity and selectivity,little is focused on the stability although the latter is of paramount importance to practical applications.In this work,we investigated the stability of Pt/WO3/Al2O3 and observed a continuous deactivation trend during a 700 h time-on-stream run.Neither the leaching of active W nor the coking was responsible for the deactivation.Instead,XRD,HAADF-STEM and CO chemisorption results clearly showed the occurrence of significant aggregation of Pt particles,which caused a remarkable decrease of Pt-WOx interfacial sites.As a consequence,strong Br?nsted acid sites which were in situ formed by H2 dissociation at the Pt-WOx interfacial sites were reduced,leading to the deactivation of the catalyst.

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.

Correlation of Deactivation of Ni-Mo-W/Al2O3 during Ultra-Low-Sulfur Diesel Production with Surface Carbon Species

The deactivation of a Ni-Mo-W/Al_2O_3 catalyst during ultra-low-sulfur diesel production was investigated in a pilot plant. The reasons of catalyst deactivation were analyzed by the methods of elemental analysis, BET and TG-MS. The results showed that the catalyst deactivation rate was notable at the beginning of run, and then gradually reached a steady state after 448 h. In the initial period the catalyst deactivation may mainly be caused by the formation of the carbon deposits. The carbon deposits blocked the catalyst pores and the accessibility of active center decreased. The TG-MS analysis identified three types of carbon species deposited on the catalysts, viz.: the low temperature carbon deposit with high H/C atomic ratio, the medium temperature carbon deposit, and the high temperature carbon with low H/C atomic ratio. The amount of high temperature carbon deposits on the catalyst determined the overall activity and, therefore the high temperature carbon was a major contributor to the deactivation of Ni-Mo-W catalyst.

Reaction and deactivation kinetics of methanol-to-olefins process based on a special TGA reactor

Thermax 700 thermo gravimetric analysis （TGA） instrument is introduced for the investigation of the reaction and deactivation kinetics of Methanol-to-Olefins （MTO） process with SAPO-34 catalyst.By the use of a special sample basket,the TGA instrument can be viewed as a plug flow fixed-bed reactor,while the weight change of SAPO-34 during reaction can be recorded online.Kinetic data are acquired in the temperature range of 648.2？748.2 K and space velocities of 7.08？35.91 h^-1 （WHSV）.Catalyst activity is expressed with average coke content,and selectivity for different products is related as a function of coke content and temperature.Methane is also introduced into the lumping kinetic model,and power exponent function with first-order reaction is adopted for model deduction.Exponential function is tested to give the best fit for catalyst activity and product selectivity with the highest correlation coefficient.The nicely agreed results between experimental and calculated data suggest that the overall kinetic model would be meaningful in both product distribution prediction and reactor simulation.