改性Cu-ZSM-11和Cu-ZSM-5分子筛催化分解一氧化氮性能

采用水热法合成法合成ZSM-11和ZSM-5分子筛,采用一步离子交换法制备了改性ZSM-11和ZSM-5系列催化剂。通过X射线衍射、电感耦合等离子体发射光谱和红外光谱对催化剂进行表征。结果表明:ZSM-5型催化剂负载的离子量高于ZSM-11型催化剂。催化剂中的共存离子Cu2+,Ce3+和Ni2+对两种类型分子筛振动所产生的影响不同,共存离子对ZSM-11的影响较大,表明2种类型分子筛骨架的结构存在差异。催化试验结果表明:Cu-ZSM-11催化剂催化稳定性高于Cu-ZSM-5催化剂。Ce3+和Ni2+改性的Cu-ZSM-11和Cu-ZSM-5催化剂的催化活性都有所提高,但Ce3+和Ni2+改性的Cu-ZSM-11催化剂的催化活性高于Cu-ZSM-11和对应的改性Cu-ZSM-5催化剂。随空速的增大,2种催化剂的催化活性先增大后减小,在空速约为0.6(g·s)/mL左右时达到最高活性。     

Decomposition of nitrous oxide in excess oxygen over Co- and Cu-exchanged MFI zeolites

The decomposition of nitrous oxide on several Co- and Cu-ZSM-5 zeolite catalysts was studied in the absence and presence of excess oxygen. Also, the effect of methane addition, as well as catalyst steaming in dry and wet feeds is reported. N₂O decomposition with no oxygen in the feed was proportional to metal loading on both catalysts. Co-ZSM-5 was much more resistant than Cu-ZSM-5 in excess oxygen. The tolerance of Co-ZSM-5 catalysts to excessive amounts of oxygen is high when Co²⁺ is stabilized in the zeolite framework and depends on the catalyst method of preparation. The presence of methane with no oxygen in the feed enhanced N₂O decomposition while the addition of both methane and oxygen to the feed decreased N₂O conversion on all catalysts tested. Co²⁺ ions stabilized by ZSM-5 framework have high hydrothermal stability in comparison to Cu²⁺ -exchanged ZSM-5.     

Designed Highly Effective Photocatalyst of Anatase TiO2 Codoped with Nitrogen and Vanadium Under Visible-light Irradiation Using First-principles

Fe/ZSM-5 and Cu-ZSM-5 were investigated for selective catalytic reduction of NO_x with ammonia. The Fe/ZSM-5 catalyst showed over 90% NO conversion from 350 to 500 °C and Cu-ZSM-5 showed over 90% NO conversion from 250 to 350 °C. After pretreatment in 10% H₂O at 700 °C, the Fe/ZSM-5 still exhibited high activities and stability. On the basis of the experiments, Fe/ZSM-5 and Cu-ZSM-5 seem to be promising candidates for diesel-engine NO_x emission control.     

Improved lean deNOx performance of Cu-ZSM-5 through alternative synthesis conditions for ZSM-5

A series of ZSM-5 samples with similar SiO₂/Al₂O₃ ratio was synthesised using different aluminum sources and by including varying amounts of calcium hydroxide during the synthesis. The samples were subsequently ion-exchanged with Cu-ions, and evaluated with respect to deNOx activity in the absence and presence of water. The choice of aluminum source and the presence of calcium hydroxide during the zeolite synthesis affected the lean deNOx activity of Cu-ZSM-5.     

Hydrothermal stabilization of ZSM-5 catalytic-cracking additives by phosphorus addition

ZSM-5 zeolites with different Si/Al ratios (15, 25, 40) were impregnated with phosphorus (0.5–3 wt%) in form of H₃PO₄ or NH₄H₂PO₄. The samples were characterized before and after severe hydrothermal treatment by XRD, IR, ²⁷Al, ²⁹Si, ³¹P MAS NMR, and their activity for the cracking of n-decane was measured. It was found that phosphorus impregnation increases the hydrothermal stability of framework aluminum whatever the source of phosphorus used. The acidity and cracking activity of steamed samples reached an optimum for a P/Al molar ratio of ca. 0.5–0.7. A chemical model for the phosphorus–zeolite interaction is proposed in which the framework aluminum pairs are stabilized by extra-framework cationic species formed by protonation of orthophosphoric acid. The influence of isolated versus pairs of aluminum on activity and selectivity after steaming is discussed. When P-impregnated ZSM-5 sample is used as an additive for cracking industrial feeds, selectivity to propylene and butenes increases.     

Time-resolved DXAFS study on the reduction processes of Cu cations in ZSM-5

The time-resolved reduction process of copper cations in/on ZSM-5 during temperature-programmed reduction (300–700 K) was studied by energy-dispersive X-ray absorption fine structure (DXAFS) as well as transmission electron microscopy (TEM). Two Cu-ZSM-5 samples with different Cu loadings were prepared by an ion-exchange method. The Cu K-edge DXAFS spectra for isolated Cu₂₊ species in the channels of ZSM-5 and CuO particles on the outer surfaces of ZSM-5 were recorded at an interval of 1 s during the reduction. The curve fitting analysis of the EXAFS data and the XANES analysis revealed that the isolated Cu₂₊ species in the channels were reduced stepwise. They were reduced to isolated Cu₊ species at 400–450 K and the Cu₊ species to Cu₀ metallic clusters at 550–650 K. Small clusters like Cu₄ were initially formed, followed by particle growth. A small part of them went out to the outer surfaces of ZSM-5 during the reduction. In contrast, CuO particles on the outer surfaces were reduced directly to Cu₀ metallic particles around 450 K.     

Phosphorus induced hydrothermal stability and enhanced catalytic activity of ZSM-5 in methanol to DME conversion

The change in properties of ZSM-5 samples was achieved by treatment with phosphorus compounds (trimethyl phosphite or phosphoric acid) and the resultant materials were characterized by N₂ adsorption, NH₃-TPD, ²⁷Al, and ³¹P MAS NMR techniques. The phosphorus-treated HZSM-5 (P/ZSM-5) samples exhibited lower acidity, higher hydrothermal stability and improved dimethyl ether (DME) selectivity in methanol conversion when compared to the phosphorus-free HZSM-5. ²⁷Al, and ³¹P MAS NMR results revealed that the added P indeed interacted with the ZSM-5 framework and is responsible for the changes observed in the catalytic properties. The interaction caused the decrease in strong acid sites on one hand and creation of new acid sites (NH₃-TPD) on the other, in P/ZSM-5 samples. The studies indicated the need of optimizing the P loading, where the positive role of P on the catalytic activity was observed to be maximum at P/Al molar ratio of 1.05.     

In situ synthesis, characterization and catalytic activity of ZSM-5 zeolites on kaolin microspheres from amine-free system

ZSM-5 zeolites were synthesized by an in situ hydrothermal crystallization method on kaolin microspheres from an organic template-free solution. The as-synthesized samples were characterized by using X-ray diffraction, scanning electron microscopy, Fourier Transform Infrared spectrometry, N₂ adsorption and desorption, and Temperature Programmed Desorption. The results showed that small-sized ZSM-5 crystallites with less than 1 micron in diameter were effectively formed on kaolin microspheres. The synthesized products indicated high hydrothermal stability and strong acidity. By mixing the H-type ZSM-5/CMK composite with a Fluid Catalytic Cracking base catalyst, the performance of the catalyst is then evaluated. The results of catalytic performance evaluation showed that with the addition of ZSM-5/CKM, it favored the production of light olefins such as propylene and butylenes by catalytic cracking of vacuum gas oil.     

Preparation effects on the activity of Cu-ZSM-5 catalysts for NO decomposition

Effects of Cu-ZSM-5 catalyst preparation on the activity of over-exchanged copper for NO decomposition are reported. The Cu-ZSM-5 catalysts were prepared by incorporating Cu²⁺ cations into ZSM-5 zeolites from an aqueous cupric acetate solution adjusted to different pH values by adding either acetic anhydride or aqueous ammonia in the solution. The Cu²⁺ exchange levels increased with increasing pH level. STEM/EDX analysis identified CuO particles (5–6 nm) on the zeolite surface for the materials exchanged at pH>6. Conversion and kinetics measurements of NO decomposition to N₂ over these catalysts showed that the over-exchanged copper was not active. Short-time wash with aqueous ammonia removed this copper. The catalyst activity correlated very well with the amount of copper remaining in the ZSM-5 channels.     

Preparation of ZSM-5 Zeolite Honeycomb Monoliths Using Microporous Silica Obtained from Metakaolinite

Zeolite honeycomb monoliths were prepared from ZSM-5 powders synthesized under hydrothermal conditions using microporous silica obtained by selective leaching of metakaolinite. This honeycomb material was compared with those prepared using alkoxides (TEOS) as the silica source. The honeycomb monoliths were formed by extrusion of paste made from the synthesized powders through a multi-channel honeycomb die. The morphology and porous properties of these materials were studied using XRD, FTIR, SEM and N₂/Ar adsorption. ZSM-5 grains in the monoliths prepared from metakaolinite showed platy morphology with preferred orientation of the crystals in the extruded surface, and displayed an absence of secondary growth. The twinned morphology of ZSM-5 crystals was observed in the monoliths prepared using TEOS and this contributed to an increase in the external surface area even though the total surface area was identical to that of samples prepared from metakaolinite. The physical properties, thermal stability and mechanical strength of the monoliths was compared with zeolite-coated honeycombs. The results show that microporous silica prepared by acid leaching of metakaolinite is a cost-effective raw material for preparing ZSM-5 honeycomb monoliths with controlled morphology and tunable SiO₂/Al₂O₃ ratios.     

Organic template-free synthesis of ZSM-5/ZSM-11 co-crystalline zeolite

A series of ZSM-5/ZSM-11 co-crystalline zeolites with various compositions and morphologies were successfully synthesized via an organic template-free hydrothermal route and characterized by XRD, XRF, SEM, NMR and N₂ adsorption/desorption technologies. The effects of raw materials and batch composition were investigated systematically. Various silicon sources can be employed in the organic template-free synthesis of ZSM-5/ZSM-11 co-crystalline zeolite, however only a few types of aluminum sources are available. This organic template-free system is favorable to the aluminum-rich zeolite. With the increase of initial SiO₂/Al₂O₃ ratio, the ZSM-5 percentage in the ZSM-5/ZSM-11 co-crystalline zeolite increases as well as the crystal size, and especially the morphology of ZSM-5/ZSM-11 co-crystalline zeolite prepared from the colloidal silica-NaAlO₂ solution system changes gradually from nano-rod aggregation, micro-spindle to single hexagon and then to twinned hexagon crystals. Moreover, Na⁺ and OH⁻ in the initial materials can promote the nucleation of the ZSM-5/ZSM-11 co-crystalline zeolite significantly and are beneficial to the formation of crystals with relatively low length/width ratio, while K⁺ postpones the crystallization process seriously.     

CuAPSO-34 Catalysts for N2O Decomposition in the Presence of H2O. A Study of Zeolitic Structure Stability in Comparison to Cu-SAPO-34 and Cu-ZSM-5

The structural stability at high temperatures of both Cu-exchanged SAPO-34 and CuAPSO-34 with isomorphously substituted copper ions has been investigated. SAPO-34 undergoes an extensive crystallinity loss upon copper ion exchange. The CuAPSO-34 framework showed good hydrothermal stability, as reflected in its surface area and X-ray diffraction pattern after ageing treatments. This catalyst exhibited good activity in N₂O decomposition even when the reaction was run in the presence of H₂O or after ageing treatment under H₂O vapor at 600 °C for 80 h which, conversely, led to a drastic loss of activity of Cu-ZSM-5.     

Ultrasound-assisted synthesis of nanosized hierarchical ZSM-5 and its catalytic performance as the support for heteropolyacid

Nanosized hierarchical micro-mesoporous ZSM-5 material has been successful synthesized using the double templating approach performed by a two-step crystallization process. The synthesis route involved static hydrothermal aging and ultrasonic-assisted aging. It was established that ZSM-5 synthesized under appropriate ultrasound stimulation possessed larger cumulative pore volume and smaller crystal size than that of samples synthesized without ultrasound stimulation. A serious of micro-mesoporous ZSM-5 supported HPW catalysts with various acid loadings were prepared by the impregnation method. The catalytic performances were investigated in the alkylation of o-xylene with styrene. Alkylation results showed that HPW/micro-mesoporous ZSM-5 exhibited better activities than that of HPW/microporous ZSM-5 catalyst. HPW-20/micro-mesoporous ZSM-5 catalyst had the best catalytic performances in terms of yield and stability, which can be attributed to its maximum medium strong acid amount and its smaller particle size which is favorable for fast diffusion of products.     

On the activity and hydrothermal stability of CuMCM-22 in the decomposition of nitrogen oxides: a comparison with CuZSM-5

A combined spectroscopic and catalytic study on the activity and hydrothermal stability of copper-exchanged MCM-22 and ZSM-5 zeolites is reported; CuMCM-22 is active in the decomposition of NO and N₂O also in the presence of water, whereas CuZSM-5 deactivates rapidly upon steaming. CO adsorption on fresh and steamed samples enlightened that the copper active species are more stable on CuMCM-22.     

A ZSM-5-based Catalyst for Efficient Production of Light Olefins and Aromatics from Fluidized-bed Naphtha Catalytic Cracking

A ZSM-5-based catalyst was prepared by spray-dry method for fluidized-bed naphtha catalytic cracking. Multi-techniques, such as X-ray diffraction, scanning electron microscope, ²⁷Al MAS NMR, and NH₃–TPD, were employed for the investigation of ZSM-5 framework stability, framework dealumination, and catalyst acidity variation in hydrothermal treatment. Catalytic performances of fluidized-bed naphtha catalytic cracking at 630–680 °C indicated that light olefins and other value-added products could be more efficiently produced compared with the commercial process of thermal steam cracking. Long-term catalytic evaluation implied that naphtha catalytic cracking over the catalyst prepared with spray-dry method and hydrothermal treatment can be carried out at a variable reaction condition with a relatively high and stable light olefins yield.     

Quantification and redox property of the oxygen-bridged Cu<Superscript>2+</Superscript> dimers as the active sites for the NO decomposition over Cu-ZSM-5 catalysts

For a range of Cu-ZSM-5 catalysts with different Cu-exchange levels on the two kinds of ZSM-5 with different Si/A1 ratios, temperature programmed reduction using CO (CO-TPR) followed by H₂ (H₂-TPR), and temperature programmed desorption of oxygen (O₂-TPD) were conducted using an online mass spectrometer to characterize and quantify the copper species on the catalysts in the calcined state. Copper species on the ZSM-5 were quantitatively characterized as Cu²⁺, (Cu-O-Cu)²⁺ and CuO after calcination in oxygen environment. The N₂ formation activities of the catalysts in the decomposition of NO were well correlated with the quantified catalytic amounts of the Cu²⁺ ions involved in the Cu-dimers, (Cu-O-Cu)²⁺. The mol fraction of the Cu ions present as the Cu-dimers increased at the sacrifice of the isolated Cu²⁺ with increasing Cu ion exchange level, suggesting that the species could be formed between the two Cu²⁺ in close proximity. Oxygen that could be thermally desorbed from the oxidized catalysts in the O₂-TPD was responsible for the reduction of the Cu-dimers. It was concluded that the decomposition of NO over Cu-ZSM-5 catalyst proceeded by the redox of (Cu-O-Cu)²⁺, as active centers. With the temperature programmed surface reaction using N₂O or NO over an oxidized catalyst sample as well as the O₂-TPD, it was possible to estimate the change of the oxidation state of the Cu ions engaged in the Cu-dimers.     

Effect of Calcination Temperature of Kaolin Microspheres on the In situ Synthesis of ZSM-5

ZSM-5 zeolite has been successfully synthesized in-situ on calcined kaolin microspheres by the hydrothermal method using n-butylamine as a template. The supported ZSM-5 was characterized by X-ray diffraction and scanning electron microscopy. The effect of calcination temperature of kaolin microspheres on the in-situ synthesis of ZSM-5 was investigated. The influence of the pretreatment temperature on the properties of kaolin microspheres including phase transformation, amounts of active SiO₂ and Al₂O₃, and pore structures, was studied using fourier transform infrared (FT-IR), nitrogen adsorption and chemical analysis. The results showed that when the calcination temperature increased from 300 to 900 °C, the amount of active SiO₂ in the kaolin microspheres increased slightly and the amount of active Al₂O₃ initially increased rapidly and then decreased steadily. The surface area and pore volume of the kaolin calcined at both low and high temperatures was less than those of kaolin calcined at a medium temperature. The property changes of kaolin caused the relative crystallinity of in situ synthesized ZSM-5 to vary.     

Chemisorption of alkenes on copper-exchanged ZSM-5 zeolite

On Cu-ZSM-5 zeolite at room temperature, propane is physisorbed, while propene shows characteristics of chemisorption. The chemisorption mode has certain advantages for the catalytic control of automotive emissions. Alkane and alkene adsorption equilibria and kinetics are compared on Cu-ZSM-5 and on ZSM-5 free of alumina. The results are discussed in terms of the Langmuir adsorption isotherm.     

Hydrothermal incorporation of Ce(La) ions into the framework of ZSM-5 by a multiple pH-adjusting co-hydrolysis

Ce and La incorporated ZSM-5 zeolitic materials with different metal loadings were synthesized via the multiple pH-adjusting procedures involving a co-hydrolysis of TEOS (tetraethyl-orthosilicate) with rare earth salts under a strong acidic condition, a further gelation under a weak acidic condition, and a final basic hydrothermal crystallization. Thus obtained Ce(La)-ZSM-5, as well as Ce or La ion-exchanged ZSM-5 samples, were characterized by XRD, SEM, TG, UV–vis, ²⁹Si MAS NMR, FT-IR, N₂-physisorption, and elemental analysis. The characterizations provide systematic and complementary evidences to demonstrate the incorporation of Ce(La) ions into the tetrahedral sites of ZSM-5 framework. The upper limits of the rare earth loadings in the synthesis gel and the final product are ca. 50 and 70 of the molar ratio of Si/Ce(La), respectively. It is observed that the synthesized Ce(La)-ZSM-5 zeolites possess an unusual morphology of microspheres that are assembled by numerous cubic prism-shaped nanocrystallines.     

Differences between ZSM-5 and ZSM-11 zeolite catalysts in 1-hexene aromatization and isomerization

ZSM-5 and ZSM-11 zeolites with high crystallinity are synthesized and tested in the aromatization and isomerization reactions of 1-hexene at 370 °C in a continuous flow fixed bed. The results indicate that ZSM-5 and ZSM-11 zeolites possess similar acid site amount and strength, and most of the acid sites belong to Brønsted acid. When the ZSM-5 and ZSM-11 zeolites were used as catalysts, the aromatics selectivity over ZSM-11 catalyst was higher than that over ZSM-5 catalyst in contrast to i-paraffins selectivity, maybe attributed to that the C₇ and C₈ aromatics have an easier exit from the ZSM-11 zeolite. Moreover, the decrease of particle size can present superior aromatics selectivity and less i-paraffins selectivity in the aromatization and isomerization of 1-hexene over the ZSM-11 catalyst.