Enhancing hydrothermal stability of nano-sized HZSM-5 zeolite by phosphorus modification for olefin catalytic cracking of full-range FCC gasoline

In this study, phosphorus modification by trimethyl phosphate impregnation was employed to enhance the hydrothermal stability of nano‐sized HZSM‐5 zeolites. A parallel modification was studied by ammonium dihydrogen phosphate impregnation. The modified zeolites were subjected to steam treatment at 800 °C for 4 h (100% steam) and employed as catalysts for olefin catalyticcracking (OCC) of full‐range fluid catalytic cracking (FCC) gasoline. X‐ray diffraction, N2 physicaladsorption and NH3 temperature‐programmed desorption analysis indicated that, although significantimprovements to the hydrothermal stability of nano‐sized HZSM‐5 zeolites can be observedwhen adopting both phosphorus modification strategies, impregnation with trimethyl phosphatedisplays further enhancement of the hydrothermal stability. This is because higher structural crystallinityis retained, larger specific surface areas/micropore volumes form, and there are greaternumbers of surface acid sites. Reaction experiments conducted using a fixed‐bed micro‐reactor(catalyst/oil ratio = 4, time on stream = 4 s) showed OCC of full‐range FCC gasoline-under a fluidized‐bed reaction mode configuration-to be a viable solution for the olefin problem of FCC gasoline.This reaction significantly decreased the olefin content in the full‐range FCC gasoline feed, andspecifically heavy‐end olefins, by converting the olefins into value‐added C2–C4 olefins and aromatics.At the same time, sulfide content of the gasoline decreased via a non‐hydrodesulfurization process.Nano‐sized HZSM‐5 zeolites modified with trimethyl phosphate exhibited enhanced catalytic performance for OCC of full‐range FCC gasoline.

Study on Hydrothermal Stability and Catalytic Activity of Al-SBA-15 Mesoporous Materials Prepared by Impregnation Method

The mesoporous Al-SBA-15 zeolite was obtained via impregnation of pure silica-based SBA-15 zeolite with aluminum nitrate.The Al-SBA-15 sample was calcined in air at 800 ℃ for 6 h and hydrothermally treated at near 100 ℃ for 120 h,respectively,and then the thermal and hydrothermal stability of Al-SBA-15 sample was investigated by X-ray diffractometry (XRD),scanning electron microscopy (SEM),transmission electron microscopy (TEM) and nitrogen adsorption and desorption techniques.The Al-SBA-15 sample was also studied by 27 Al nuclear magnetic resonance (27 Al NMR) and ammonia temperature programmed desorption (NH 3-TPD) techniques.In addition,the catalytic activity of Al-SBA-15 zeolite was investigated by the Friedel-Crafts reactions of 2,4-di-tert-butylphenol with cinnamyl alcohol.The test results showed that the thermal and hydrothermal stability of Al-SBA-15 zeolite was better than that of SBA-15 zeo-lite.The Al-SBA-15 zeolite sample prepared by impregnation method exhibits more framework aluminum species and Al-O-Si units.Therefore,the number of the surface hydroxyl groups was reduced,resulting in the stabilization of framework structure ofAl-SBA-15 zeolite.The aluminum species can form weak and medium-strong acid sites with catalytic activity.

A reconstruction strategy for the synthesis of Cu-SAPO-34 with excellent NH-SCR catalytic performance and hydrothermal stability

A reconstruction strategy has been developed to synthesize Cu-SAPO-34 with a wide crystallization phase region,high solid yield,and tunable Si and Cu contents.Cu-rich SAPO-34 was prepared from a Cu-amine complex,which acted as a precursor and Cu source for the reconstruction synthesis.The role of the Cu-amine complex as a template was restricted,which allowed easier control over the Cu and Si contents than in the previously reported"one-pot"synthesis method.Characterization of the material revealed that the Si(4Al)coordination environment dominates the synthesized Cu-SAPO-34 catalysts.High-temperature hydrothermal treatment increased the isolated Cu2+content slightly,and the acid sites in the low-silica catalyst are more resistant to hydrothermal treatment than those of the existing catalysts.The obtained materials,especially the low-silica Cu-SAPO-34 sample,exhibit excellent catalytic activity and hydrothermal stability for the selective catalytic reduction of NOx by NH3(NH3-SCR).In addition,the influence of the catalyst acidity on the NH3-SCR reaction was also investigated and is discussed.The high synthetic efficiency and outstanding catalytic performance make Cu-SAPO-34 synthesized by the reconstruction method a promising catalyst for the NH3-SCR process.

Gas separation using sol–gel derived microporous zirconia membranes with high hydrothermal stability

A microporous zirconia membrane with hydrogen permeance about 5 × 10-8mol·m-2·s-1·Pa-1, H2/CO2 permselectivity of ca. 14, and excellent hydrothermal stability under steam pressure of 100 k Pa was fabricated via polymeric sol–gel process. The effect of calcination temperature on single gas permeance of sol–gel derived zirconia membranes was investigated. Zirconia membranes calcined at 350 °C and 400 °C showed similar single gas permeance, with permselectivities of hydrogen towards other gases, such as oxygen, nitrogen, methane, and sulfur hexa fluoride, around Knudsen values. A much lower CO2permeance（3.7 × 10-9mol·m-2·s-1·Pa-1）was observed due to the interaction between CO2 molecules and pore wall of membrane. Higher calcination temperature, 500 °C, led to the formation of mesoporous structure and, hence, the membrane lost its molecular sieving property towards hydrogen and carbon dioxide. The stability of zirconia membrane in the presence of hot steam was also investigated. Exposed to 100 k Pa steam for 400 h, the membrane performance kept unchanged in comparison with freshly prepared one, with hydrogen and carbon dioxide permeances of 4.7 × 10-8and ~ 3 × 10-9mol·m-2·s-1·Pa-1, respectively. Both H2 and CO2permeances of the zirconia membrane decreased with exposure time to 100 k Pa steam. With a total exposure time of 1250 h, the membrane presented hydrogen permeance of 2.4 × 10-8mol·m-2·s-1·Pa-1and H2/CO2 permselectivity of 28, indicating that the membrane retains its microporous structure.

Synthesis of Ordered Cubic Periodic Mesoporous Silica with High Hydrothermal Stability

1 Introduction Since its first discovery in 1992, ordered mesoporous silica material with large pore size, high surface area, and high pore volume has attracted great attention for the potentially wide application in catalysis, adsorption, separation, and ion exchange, etc. However, the poor hydrothermal stability of mesoporous silica has limited its wide application in industry. Therefore, in the last 10 years, many studies have been dedicated to improving the hydrothermal stability of mesoporous silica. Xiao et al.

Effects of impregnation sequence on the NH_(3)-SCR activity and hydrothermal stability of a Ce-Nb/SnO_(2) catalyst

Hydrothermal stability is crucial for the practical application of deNO_(x)catalyst on diesel vehicles,for the selective catalytic reduction of NO_(x)with NH_(3)(NH_(3)-SCR).SnO_(2)-based materials possess superior hydrothermal stability,which is attractive for the development of NH_(3)-SCR catalyst.In this work,a series of Ce-Nb/SnO_(2)catalysts,with Ce and Nb loading on SnO_(2)support,were prepared by impregnation method.It was found that,the NH_(3)-SCR activities and hydrothermal stabilities of the Ce-Nb/SnO_(2)catalysts significantly varied with the impregnation sequences,and the Ce-Nb(f)/SnO_(2) catalyst that firstly impregnated Nb and then impregnated Ce exhibited the best performance.The characterization results revealed that CeNb(f)/SnO_(2)possessed appropriate acidity and redox capability.Furthermore,the strong synergistic effect between Nb and Sn species stabilized the structure and maintained the dispersion of acid sites.This study may provide a new understanding for the effect of impregnation sequence on activity and hydrothermal stability and a new environmental-friendly NH_(3)-SCR catalyst with potential applications for NO_(x)removal from diesel and hydrogenfueled engines.

Innovative construction of macroporous–mesoporous structured spherical alumina and its hydrothermal stability

The pore structure of spherical alumina supports is closely related to the dispersion of catalytically active components and the diffusion of reactants.Maintaining excellent pore structure under strict reaction conditions is of utmost importance.In this work,sphericalγ-Al_(2)O_(3)support with a bimodal pore structure,composed of macropores and mesopores,was successfully synthesized using dodecane as the pore-forming agent through the oil–ammonia column-shaping method.The morphology and internal pore structure of the alumina were found to be influenced by the amount of surfactant added and ultrasound treatment conditions.Notably,when concentration of surfactant was 4‰and ultrasound voltage of 20 V was applied,the resultingγ-Al_(2)O_(3)-4‰-20 displayed a highly concentrated distribution of macropores with an average pore size of 100 nm,resulting in an impressive porosity of 69.21%.In contrast,the untreated sample ofγ-Al_(2)O_(3)-0-0 only exhibited a mesoporous distribution with a porosity of 54.03%.Moreover,after being subjected to a hydrothermal treatment in a high temperature(600°C)and high humidity(water vapor)environment for 120 h,theγ-Al_(2)O_(3)-4‰-20 sample maintained a high BET specific surface area of 170.9 m^(2)g^(−1)and mercury intrusion porosimetry specific surface area of 263.3 m^(2)g^(−1).

Promotional effect of ion-exchanged K on the low-temperature hydrothermal stability of Cu/SAPO-34 and its synergic application with Fe/Beta catalysts

K ions were introduced onto Cu/SAPO-34 catalysts via the ion-exchange process in order to improve their stability under low-temperature hydrothermal aging.The changes in structure and copper-species contents of these catalysts upon hydrothermal aging were probed in order to investigate their effects on selective catalytic reduction(SCR)activity.For the fresh Cu/SAPO-34 catalysts,K ions had little influence on the chabazite framework but effected their acidities by exchanging with acid sites.After hydrothermal aging,the structural integrity and amount of active sites decreased on pure Cu/SAPO-34.While the K-loaded catalysts showed improved chabazite structure,acidity,and active site conservation with increasing K loading.However,although the 0.7 wt%K catalyst maintained the same crystallinity,active site abundance,and low-temperature SCR activity as the fresh catalyst upon aging,an apparent decrease in SCR activity at high temperature was observed because of the inevitable decrease in the number of Brönsted acid sites.To compensate for the activity disadvantage of K-loaded Cu/SAPO-34 at high temperature,Fe/Beta catalysts were co-employed with K-loaded Cu/SAPO-34,and a wide active temperature window of SCR activity was obtained.Thus,our study reveals that a combined system comprising Fe/Beta and K-loaded Cu/SAPO-34 catalysts shows promise for the elimination of NOx in real-world applications.

Possible negative influences of increasing content of cerium on activity and hydrothermal stability of Rh/ceria-zirconia three-way catalysts

The activity and hydrothermal stability of the Rh/Ce_(x)Zr_(1-x)O_(2)(x=0,0.05,0.3,0.5) model three-way catalysts for gasoline vehicle emissions control were investigated in this work.Among the Rh/Ce_(x)Zr_(1-x)O_(2) samples with different Ce/Zr ratios,the Rh/ZrO_(2) sample exhibits a significantly better activity and hydrothermal stability than the rest of the samples.The impacts of having more Ce components in the Rh/Ce_(x)Zr_(1-x)O_(2) catalysts are associated with the strong Rh-O-Ce interaction that tends to over stabilize the rhodium species.A significant amount of such rhodium atoms can be found in the bulk of the support oxides after a hydrothermal aging at 1050℃ with 10% H_(2)O in air for 12 h.Differently,the sintering of rhodium on the surface of Rh/ZrO_(2) catalysts is the main reason for the catalyst deactivation during the hydrothermal aging.These findings provide an example where high dispersion of supported metal induced by strong metal-support interactions does not necessarily lead to high catalytic activity.

Nature of cerium on improving low-temperature hydrothermal stability of SAPO-34

To probe the function of Ce on enhancing low-temperature stability of SAPO-34,Ce/SAPO-34 with different Ce contents was prepared via one-pot method and further treated at 70℃in 80%relative humidity for 24 h.The structural results prove that the one-pot synthesis is an effective way to introduce Ce(Ce<0.325 wt%)without influencing micro-structural and chemical composition.The lowtemperature hydrothermal stability of Ce/SAPO-34 is enhanced by Ce loading.More than 92%CHA structure and total acidity are maintained over 0.188 wt%Ce/SAPO-34,while only about 20%of that left on pure H/SAPO-34.As Ce exists as Ce^(3+)at exchange sites on the surface of SAPO-34,the results of the linear relationship between protected surface acidity and structure/acidity conservation manifest that Ce^(3+))effectively hinders the structural collapse.This study provides new insight into surface acidity protection for solving the problem of low-temperature hydrothermal stability of SAPO-34.

Activity and hydrothermal stability of CeO_2–ZrO_2–WO_3 for the selective catalytic reduction of NO_x with NH_3

A series of CeO2–ZrO2–WO3（CZW）catalysts prepared by a hydrothermal synthesis method showed excellent catalytic activity for selective catalytic reduction（SCR）of NO with NH3 over a wide temperature of 150–550℃.The effect of hydrothermal treatment of CZW catalysts on SCR activity was investigated in the presence of 10% H2O.The fresh catalyst showed above 90% NOx conversion at 201–459℃,which is applicable to diesel exhaust NOx purification（200–440℃）.The SCR activity results indicated that hydrothermal aging decreased the SCR activity of CZW at low temperatures（below 300℃）,while the activity was notably enhanced at high temperature（above 450℃）.The aged CZW catalyst（hydrothermal aging at 700℃ for 8 hr）showed almost 80% NOx conversion at 229–550℃,while the V2O5–WO3/TiO2 catalyst presented above 80% NOx conversion at 308–370℃.The effect of structural changes,acidity,and redox properties of CZW on the SCR activity was investigated.The results indicated that the excellent hydrothermal stability of CZW was mainly due to the CeO2–ZrO2 solid solution,amorphous WO3 phase and optimal acidity.In addition,the formation of WO3 clusters increased in size as the hydrothermal aging temperature increased,resulting in the collapse of structure,which could further affect the acidity and redox properties.

Enhanced hydrothermal stability of Cu-SAPO-34 with an ultrathin TiO_(2)coated by atomic layer deposition for NH3-SCR

Reducing pollution and carbon emissions is an important step toward peaking CO_(2)emissions before 2030 and reaching carbon neutrality before 2060,and heavy diesel vehicle pollution,particularly nitrogen oxides(NOx)emissions,is an essential part.CuSAPO-34 is a CHA-type small pore molecular sieve with excellent ammonia(NH_(3))selective catalytic reduction(NH_(3)-SCR)catalytic activity,but it cannot be stored or applied because of severe degradation caused by low-temperature hydrothermal aging.To improve the hydrothermal stability,TiO_(2)was coated on the surface of Cu-SAPO-34 by the ALD method to form a uniform nanolayer.Though this ultrathin TiO_(2)nanolayer has little effect on NH_(3)-SCR catalytic activity of Cu-SAPO-34,the resistance to low-temperature hydrothermal aging in liquid water at 80℃for 24 h has greatly been improved.A study carried out by SEM,XRD,NH_(3)-TPD,and EPR,showed that the ultra-thin TiO_(2)nanolayers were covered uniformly and hydrolysis of frameworks silicon and the migration of Cu^(2+)was retarded.This method has some implications for the future preparation of highly robust Cu-SAPO-34 catalysts for industrial applications.This research could inspire the development of highly robust CuSAPO-34 catalysts to control the NOx emissions from diesel engines.

Catalytic hydrothermal liquefaction of microalgae over metal incorporated mesoporous SBA-15 with high hydrothermal stability

Hydrothermal liquefaction(HTL)is one of the most promising technologies for conversion of microalgae,and catalysts with high hydrothermal stability are required for controllable HTL.In this article,SBA-15 incorporated with transition metals(Ni,Pd,Co and Ru)were synthetized via double-template method for catalytic HTL of microalgae.The results showed that metal incorporated SBA-15 represented high hydrothermal stability at 613 K.The incorporated Ni,Co and Ru was dispersed in SBA-15 enhancing the hydrothermal stability.The catalysts greatly influenced the chemical composition of the obtained bio-oil,which contained a higher percentage of furfural derivatives and a lower content of fatty acids and N-containing compounds,thus bio-oil quality was improved significantly.Higher hydrothermal stability and specific surface areas of Co-SBA-15 contribute to the highest preformation with 78.78%conversion and 24.11 wt%bio-oil yield.Metal incorporated SBA-15 provides a potential application for biomass conversion in high-temperature aqueous phase.

Hydrothermal stability of MO_x-Ce_(0.75)Zr_(0.25)O_2 catalysts for NO_x reduction by ammonia

Various acidic components（MOx：phosphate,sulfate,tungstate and niobate） were loaded on Ce0.75 Zr0.25 O2 powders by an impregnation method.The as-prepared catalysts were hydrothermally treated at 760 oC for 48 h in air containing 10 vol.% H2 O to obtain the aged catalysts.The catalysts were characterized by X-ray diffraction,Fourier transform infrared spectroscopy,H2 programmed-reduction,NH3 adsorption and deNOx activity measurements.The results showed that,among the catalysts investigated,the phosphated Ce0.75 Zr0.25 O2 catalyst showed the highest hydrothermal stability.The remained high acidity of the phosphated catalyst with moderate redox property helped to maintain the excellent NH3-SCR activity of hydrothermally aged catalyst.Cerium tungstate led to the poor redox property of the tungstated catalyst although the acidity of catalyst was still high.The decomposition of sulfates at temperatures higher than 600 °C restrained the usage of sulfated catalysts in high temperature conditions.The overall dehydration of niobate to niobium oxides led to the low acidity of hydrothermally aged Nb2 O5-Ce0.75 Zr0.25 O2 catalyst.

Optimization of Hybrid Crystal with SAPO-5/34 on Hydrothermal Stability for deNOx Reaction by NH3

In order to deal with the challenge of the hydrothermal deactivation of selective catalytic reduction of NO by NH3(NH3-SCR)catalyst and extend its lifetime,a novel Cu/SAPO-5/34 catalyst was prepared,and it almostmaintains its deNOx performance with a high conversion rate of 90%NO,between 175℃and 400℃after under-going the rigorous treatment at 800℃for 12 h.Thus,Cu/SAPO-5/34 is more recalcitrant to the high-temperature hydrothermal deactivation than Cu/SAPO-34.Besides,the formation of N20 is always below 3×10^-6(3 ppm)during the whole reaction temperature.performing an advanced catalytic selectivity.The effect of high-temperature hvdro-thermal treatment on the morphology,structure and texture property,the acid sites,as well as the active copper spe cies were investigated.These characterizations manifest that the optimized high-temperature hydrothermal stability is associated closely with the good structural stability over Cu/SAPO-5/34-HT.which facilitates to preserve reaction sites,and then showing the better hydrothermal stability than Cu/SAPO-34.

Effects of silica additive on the NH_3-SCR activity and thermal stability of a V_2O_5/WO_3-TiO_2 catalyst

V2O5/WO3‐TiO2 and V2O5/WO3‐TiO2‐SiO2 catalysts were prepared by a wetness impregnation method, and both the catalysts were hydrothermally aged at 750℃ in 10 vol%H2O/air for 24 h. The catalysts were evaluated for NOx conversion using NH3 as the reductant. Hydrothermal ageing decreased the NOx conversion of V2O5/WO3‐TiO2 catalyst severely over the entire measured tem‐perature range. Interestingly, the NH3‐SCR activity of the silica‐modified catalyst at 220–480℃ is enhanced after ageing. The catalysts were characterized by X‐ray diffraction, nitrogen adsorption, X‐ray fluorescence, Raman spectroscopy, H2 temperature‐programmed reduction, and NH3 temper‐ature‐programmed desorption. The addition of silica inhibited the phase transition from anatase to rutile titania, growth of TiO2 crystallite size and shrinkage of catalyst surface area. Consequently, the vanadia species remained highly dispersed and the hydrothermal stability of the V2O5/WO3‐TiO2 catalyst was significantly improved.

Stability of Cu-Mn bimetal catalysts based on different zeolites for NO_x removal from diesel engine exhaust

Cu–Mn bimetal catalysts were prepared to remove nitrogen oxides(NOx)from diesel engine exhaust at low temperatures.At a Cu/Mn ratio of 3:2,the NOx conversions at 200°C reached 65%and 90%on Cu–Mn/ZSM‐5 and Cu–Mn/SAPO‐34,respectively.After a hydrothermal treatment and reaction in the presence of C3H6,the activity of Cu–Mn/SAPO‐34 was more stable than that of Cu–Mn/ZSM‐5.No obvious variations in the crystal structure or dealumination were observed,whereas the physical structure was best maintained in Cu–Mn/SAPO‐34.The atomic concentration of Cu on the surface of Cu–Mn/SAPO‐34 was quite stable,and the consumption of octahedrally coordinated Cu2+could be recovered.Conversely,the proportion of octahedrally coordinated Cu2+on the surface of Cu–Mn/ZSM‐5 significantly decreased.Therefore,besides the structure,the redox cycle between Cu+and octahedrally coordinated Cu2+played an important role in the stability of the catalysts.

Thermal and hydrothermal stabilities of the alkali-treated HZSM-5 zeolites

HZSM-5 zeolites with the micro-mesopore hierarchical porosity have been prepared by the post-synthesis of alkali-treatment, and their thermal and hydrothermal stabilities were studied using DTA, XRD, and NH3-TPD characterization techniques. Compared to the unmodified zeolite, the thermal and hydrothermal stabilities of the alkali-treated ZSM-5 zeolites were slightly deteriorated because of the introduction of mesopores caused by the desilication. Nevertheless, the alkali-treated zeolite framework could be maintained until the temperature increased to 1175 ℃.

One-step post-synthesis treatment for preparing hydrothermally stable hierarchically porous ZSM-5

Hierarchically porous ZSM‐5 (SiO2/Al2O3 ≈ 120) containing phosphorus was prepared by a one‐step post‐synthesis treatment involving controlled desilication and phosphorous modification. The hierarchically porous ZSM‐5 featured high thermal and hydrothermal stability. The obtained ZSM‐5zeolites were systematically characterized by X‐ray diffraction, scanning electron microscopy,transmission electron microscopy, N2 adsorption‐desorption, NH3 temperature‐programmed desorption,and 27Al and 31P magic‐angle spinning nuclear magnetic resonance spectroscopy. Theprepared ZSM‐5 displayed enhanced activity and prolonged lifetime toward hydrocarbon cracking.The high activity was attributed to improved coke tolerance owing to the presence of the highlystable mesoporous network of ZSM‐5 and acid sites introduced upon phosphorus modification.Additionally a mechanism of the stabilization of the zeolites by phosphorus was proposed and discussed.

Synthesis of AIMCM-41 mesoporous molecular sieves with high stability

Mesoporous molecular sieves AIMCM-41 were synthesized by static hydrothermal crystallization using cetyltrimethylammonium bromide as template, water glass as silica source and pseudoboehmite as aluminum source. The XRD results showed that the prepared AlMCM-41 mesoporous molecular sieves had high relative crystallinity and long-range order. The relative crystallinity was greater than 27% after calcination at 900 ℃ for 2 hours and was still greater than 14% after ageing in steam at 800 ℃ for 2 hours. The results indicated that both thermal and hydrothermal stabilities of the mesoporous molecular sieves AIMCM-41 were good.