Mechanism of Metal Deactivators

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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.

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.

Effect of Fe Addition on Dehydrogenation Performance of Methylcyclohexance over Pt/Al_(2)O_(3)

Catalysts with varying Fe contents were prepared using a sequential impregnation method to investigate the effects of Fe addition on the physicochemical properties of Pt/Al_(2)O_(3) and their performance in methylcyclohexane(MCH)dehydrogenation.The results demonstrated that the addition of Fe to Pt/Al_(2)O_(3) enhanced the electron density of Pt and improved catalytic activity,while exhibiting negligible influence on the catalytic selectivity for toluene.When the Fe content was 0.057%,the catalyst exhibited the highest MCH consumption rate,which was approximately two times higher than that of the catalyst without Fe.Additionally,the incorporation of Fe inhibited the formation of coke and reduced the quantity of coke deposits on the catalyst,thereby improving its catalytic durability.Overall,Fe shows promise as a prospective secondary element for Pt/Al_(2)O_(3) to enhance the MCH dehydrogenation performance.

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.

Probing deactivation by coking in catalyst pellets for dry reforming of methane using a pore network model

Dry reforming of methane(DRM) is an attractive technology for utilizing the greenhouse gases(CO_(2) and CH_(4)) to produce syngas. However, the catalyst pellets for DRM are heavily plagued by deactivation by coking, which prevents this technology from commercialization. In this work, a pore network model is developed to probe the catalyst deactivation by coking in a Ni/Al_(2)O_(3) catalyst pellet for DRM. The reaction conditions can significantly change the coking rate and then affect the catalyst deactivation. The catalyst lifetime is higher under lower temperature, pressure, and CH_(4)/CO_(2) molar ratio, but the maximum coke content in a catalyst pellet is independent of these reaction conditions. The catalyst pellet with larger pore diameter, narrower pore size distribution and higher pore connectivity is more robust against catalyst deactivation by coking, as the pores in this pellet are more difficult to be plugged or inaccessible.The maximum coke content is also higher for narrower pore size distribution and higher pore connectivity, as the number of inaccessible pores is lower. Besides, the catalyst pellet radius only slightly affects the coke content, although the diffusion limitation increases with the pellet radius. These results should serve to guide the rational design of robust DRM catalyst pellets against deactivation by coking.

Oxidation of benzene to phenol with N_(2)O over a hierarchical Fe/ZSM-5 catalyst

Catalytic oxidation of benzene with N_(2)O to phenol over the hierarchical and microporous Fe/ZSM-5-based catalysts in a continuous fixedbed reactor was investigated.The spent catalyst was in-situ regenerated by an oxidative treatment using N_(2)O and in total 10 reaction-regeneration cycles were performed.A 100% N_(2)O conversion,93.3% phenol selectivity,and high initial phenol formation rate of 16.49±0.06mmol_(phenol gcatalyst)^(-1)h^(-1)at time on stream(TOS) of 5 min,and a good phenol productivity of 147.06 mmol_(phenol gcatalyst)^(-1)during catalyst lifetime of 1800 min were obtained on a fresh hierarchical Fe/ZSM-5-Hi2.8 catalyst.With the reaction-regeneration cycle,N_(2)O conversion is fully recovered within TOS of 3 h,moreover,the phenol productivity was decreased ca.2.2±0.8% after each cycle,leading to a total phenol productivity of ca.0.44 ton_(pheol kg_(catalyst)^(-1)estimated for 300 cycles.Catalyst characterizations imply that the coke is rapidly deposited on catalyst surface in the initial TOS of 3 h(0.28 mgc_(gcatalyst)^(-1)min^(-1)) and gradually becomes graphitic during the TOS of 30 h with a slow formation rate of 0.06 mgc g_(catalyst)^(-1)min^(-1).Among others(e.g.,the decrease of textural property and acidity),the nearly complete coverage of the active Fe-O-Al sites by coke accounts for the main catalyst deactivation.Besides these reversible deactivation characteristics related to coking,the irreversible catalyst deactivation is also observed with the reaction-regeneration cycle.The latter is reflected by a further decreased amount of the active Fe-O-Al sites,which agglomerate on catalyst surface with the cycle,likely associated with the hard coke residue that is not completely removed by the regeneration.

Elucidating the effect of oxides on the zeolite catalyzed alkylation of benzene with 1-dodecene

In the present work, the effect of oxides on the alkylation of benzene with 1-dodecene was comprehensively investigated over MCM-49 n-heptanol, n-heptaldehyde and n-heptanoic acid were selected as the model oxides herein, and obvious decrease of lifetime could be caused by only trace amount of oxides added in the feedstocks. However, the deactivated catalysts were difficult to be regenerated by extraction with hot benzene. Additionally, coke-burning was also proved to be incapable to regenerate the deactivated catalysts mainly for the dealumination during calcination. Further characterizations complementary with DFT calculations were conducted to demonstrate that the deactivation was mainly due to the firm adsorption of oxides on the acid sites.

Experiment and modeling of coke formation and catalyst deactivation in n-heptane catalytic cracking over HZSM-5 zeolites

Since paraffins catalytic cracking was of significant importance to light olefins and aromatics production,this work was intended to gain insights into the feature and model of coke formation and catalyst deactivation in n-heptane catalytic cracking over HZSM-5 zeolites. 18 tests of n-heptane catalytic cracking were designed and carried out over HZSM-5 zeolites in a wide range of operating conditions. A particular attention was paid to the measurement of the conversion, product distribution, coke content, and the porosity and acidity of the fresh and spent HZSM-5 zeolites. It was found that alkene and aromatic promoted coke formation, and it reduced the pore volume and acid site of HZSM-5 zeolites, tailoring its performance in n-heptane catalytic cracking. The specific relationship between HZSM-5 zeolites, n-heptane conversion, product distribution and coke formation was quantitively characterized by the exponential and linear function. Based on the reaction network, the coupled scheme of coke formation and catalyst deactivation were specified for n-heptane catalytic cracking. The dual-model was proposed for the process simulation of n-heptane catalytic cracking over HZSM-5 zeolites. It predicted not only the conversion and product distribution but also coke content with the acceptable errors.

Rational design of MoS_(2)-based catalysts toward lignin hydrodeoxygenation:Interplay of structure,catalysis,and stability

The MoS_(2)-based materials are a vital class of heterogeneous catalysts for the hydrodeoxygenation of lignin and its model compounds to produce value-added chemicals especially because of their unique selectivity to aromatics.The rational design of MoS_(2)-based catalyst greatly depends on the comprehensive understanding of its structure-activity relationship.However,an intensive summary and critical analysis are still scarce to date.In this review,we attempt to provide an in-depth understanding of the interplay of structure,catalysis,and stability of MoS_(2)-based catalysts for lignin hydrodeoxygenation.The recognition of intrinsic active sites on MoS_(2) structure was firstly discussed,followed by the illustration of MoS_(2)-catalyzed hydrodeoxygenation structural models.Afterward,based on the studies on the MoS_(2)-catalyzed lignin model compounds hydrodeoxygenation,the current active site modification strategies including structural modification of monometallic MoS_(2) catalysts and collaborative modification were summarized and emphatically discussed,which aims to elucidate the structure-activity relationship at the atomic-level.The deactivation mechanism and stabilization strategies were also illustrated to provide instructive suggestion for the rational design of efficient and stable MoS_(2)-based catalysts.Finally,the real lignin depolymerization over MoS_(2)-based catalysts was summarized to point out the advantages and difficulties.This review attempts to highlight the remaining challenges and provide some perspectives for the future development of MoS_(2)-based catalysts for lignin hydrodeoxygenation.

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.

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.

Studies on polyoxymethylene dimethyl ethers production from dimethoxymethane and 1,3,5-trioxane over SO_(4)^(2-)/ZrO_(2)-TiO_(2)

Polyoxymethylene dimethyl ethers(OMEs)with physical properties similar to those of diesel has received significant attention as green additives for soot emission suppression.Herein,series of SO_(4)^(2-)/ZrO_(2)-TiO_(2)catalysts were developed for OMEs production from dimethoxymethane(DMM)and1,3,5-trioxane through sequential formaldehyde monomer insertion into C-O bond of DMM.Not Lewis but Bronsted acid sites were identified to be active for the decomposition of 1,3,5-trioxane into formaldehyde unit,however,both of them are effective for the chain propagation of DMM via formaldehyde unit insertion into C-O bond.Kinetic studies indicated each chain growth step exhibited the same parameters and activation barrier on corresponding Bronsted and Lewis acid sites due to the same reaction mechanism and very similar chemical structure of OMEs.Also,the catalytic stability investigation suggested the deactivation behavior was derived from the carbon deposition,and the decay factor could be exponentially correlated with the amount of coke accumulation.

Hydroisomerization of n-Pentane over Zn-Fe-S2O8-2/ZrO2-Al2O3 Superacid Catalyst: Activity, Surface Analysis and the Investigation of Deactivation and Regeneration

The Zn and Fe modified /ZrO2-Al2O3 catalyst (Zn-Fe-SZA) was prepared and mechanisms of deactivation and methods for regeneration of as-prepared catalyst were explored with n-pentane isomerization as a probe reaction. The results indicated that the isopentane yield of the fresh Zn-Fe-SZA-F catalyst was about 57% at the beginning of the run, and declined gradually to 50% within 1500 min, then fell rapidly from 50% to 40% between 1500 and 2500 minutes. The deactivation of Zn-Fe-SZA catalyst may be caused by carbon formation on surface of the catalyst, sulfate group attenuation owing to reduction by hydrogen, removal of sulfur species and the loss of strong acid sites. It was found that the initial catalytic activity over Zn-Fe-SZA-T catalyst was 48%, which recovered by 84.3% as compared to that of fresh catalyst (57%). However, it showed a sharp decrease in isopentane yield from 48% to 29% within 1500 minutes, showing poor stability. This is associated to the loss of acidity caused by removal of sulfur species cannot be basically restored by thermal treatment. Resulfating the calcined catalyst could improve the acidity of catalyst significantly, especially strong acid sites, as compared with the calcined sample. The improved stability of the resulfated catalyst can be explained by: 1) eliminaton of carbon deposition to some extent by calcination process, 2) formation of improved acidic nature by re-sulfation, favoring isomerization on acidic sites, 3) restructuring of the acid and metal sites via the calcination-re-sulfation procedure.

Cartilage Wear in Healthy and Osteoarthritis Joints

This study is designed to determine whether the outermost layer of articular cartilage is deficient in Osteoarthritis (OA). Phospholipids present in healthy and osteoarthritis (OA) synovial fluid show significant differences in their concentration. While examining the surface properties of OA joints, we found that OA PLs molecules cannot support lubrication, and increased friction was observed. Our lubrication mechanism was based on a surface active phospholipids (SAPL) multibilayer which in OA condition was deactivated and removed from the cartilage surface under OA conditions. Cartilage wettability study clearly demonstrated a significant decrease in hydrophobicity, the contact angle, θ (theta), dropping from 103° from bovine healthy cartilage to 65° in surface partially depleted and 35.1° for completely depleted surface. These results are discussed in the context that surface active phospholipid (SAPL) and lubricin, each has specific roles in a lamellar-repulsive lubrication system. However, deactivated phospholipid molecules are major indicator of cartilage wear (model) introduced in this study.

碱性去活柱反相高效液相色谱法分析红霉素肟及相关化合物

采用碱性去活（BDS）C18柱分离测定了红霉素肟及相关化合物。以0．02mol／L磷酸氢二钾（用磷酸调pH7．2）-乙腈-甲醇（体积比为50：40：10）为流动相，检测波长为210nm，柱温为35℃。红霉素肟E、Z异构体及相关化合物红霉素A、红霉素A8，9-脱水-6，9-半缩酮和红霉素A6，9-9，12-螺缩酮五种组分分离完全，检测限（S/N=3）为6．0～24．0ng，线性关系良好，方法准确可靠，用于实际样品分析时取得较好的效果。

分层实体制造(LOM)成形过程中的热力耦合有限元分析

在分层实体制造（LOM工艺）过程中，原型件存在着翘曲变形的问题，采用热力耦合的有限元分析方法对LOM成形过程进行分析，为优化工艺参数、获得高精度的原型件提供依据。在有限元分析过程中，针对LOM成形过程的特殊性，对其材料模型的选取、材料增长过程的描述、动态的边界条件等进行了特别的处理。采用了单元的activate/deactivate技术来对LOM成形过程的材料增长过程进行描述。

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.

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.