Bifunctional mesoporous Cu–Al–MCM-41 materials for the simultaneous catalytic abatement of NOx and VOCs

This study explored the possibility of using waste organic solvent as the source of volatile organic compound (VOC) and it served as a reducing agent of selective catalytic reduction (SCR) deNO_x process, in which the VOC itself can be catalytically oxidized on the mesoporous Cu and/or Al substituted MCM-41 catalysts. The synthesized Cu–Al–MCM-41 catalysts were extensively characterized by powder low-angle X-ray diffraction (XRD), N₂ adsorption–desorption measurements, transmission electron microscopy (TEM), UV–Visible diffuse reflectance spectroscopy (UV–Vis DRS), ²⁷Al magic angle spinning-nuclear magnetic resonance spectroscopy (MAS-NMR), electron paramagnetic resonance spectroscopy (EPR) and inductively coupled plasma–mass spectrometer (ICP–MS) analysis. The XRD, TEM and N₂ adsorption–desorption studies clearly demonstrated the presence of a well ordered long range hexagonal array with uniform mesostructures. The Cu–Al–MCM-41 materials showed a better long-term-stability than that of copper ion-exchanged H–ZSM-5 (Cu–ZSM-5) zeolite. The Cu–Al–MCM-41 material was found to be an efficient catalyst than that of Cu–MCM-41 without aluminum for the simultaneous catalytic abatement of NO_x and VOCs, which was attributed to the presence of well dispersed and isolated Cu²⁺ ions on the Cu–Al–MCM-41 catalyst as observed by UV–Vis DRS and EPR spectroscopic studies. And the presence of aluminum (Al³⁺ ions) within the framework of Cu–Al–MCM-41 stabilized the isolated Cu²⁺ ions thus it led to higher and stabilized activity in terms of NO_x reduction.     

Fe-ZSM-5 for Selective Catalytic Reduction of NO with NH3: A Comparative Study of Different Preparation Techniques

Fe-ZSM-5 are prepared by using four different techniques: conventional aqueous ion-exchange (CA), improved aqueous ion-exchange (IA), solid-state ion-exchange (SS) and chemical vapor ion-exchange (CV). All of the catalysts show very high activities for selective catalytic reduction (SCR) of NO with ammonia. However, the activities are different and follow the sequence of Fe-ZSM-5 (IA) > Fe-ZSM-5 (CA), Fe-ZSM-5 (SS) > Fe-ZSM-5 (CV). ESR results indicate that Fe³⁺ ions with tetrahedral coordination are the active sites for the SCR reaction.     

Characterization of the Active Sites on Pt-Loaded ZSM-5 (Pt/ZSM-5) Prepared by an Ion-Exchange Method for the Oxidation of CO at Low Temperatures

Highly dispersed Pt-loaded ZSM-5 (Pt/ZSM-5) catalysts were prepared by a combination of ion-exchange and thermal pretreatment in different temperatures under vacuum. Highly dispersed ion-exchanged Pt²⁺ ions were reduced into Pt⁺ and then Pt⁰, sustaining their high dispersion state with an increase in the thermal pretreatment temperatures up to 773 K. Thus, prepared Pt⁰ highly dispersed in the cavities of ZSM-5 exhibited high catalytic activity for the oxidation of CO with N₂O at 273?K. However, pretreatment at temperatures higher than 973 K led to the aggregation of highly dispersed Pt⁰ clusters, resulting in a decrease in the catalytic activity for low-temperature oxidation.     

Utilization of ZSM-5/MCM-41 composite as FCC catalyst additive for enhancing propylene yield from VGO cracking

A micro-mesoporous ZSM-5/MCM-41 composite molecular sieve (ZM13) was synthesized and tested as an FCC catalyst additive to enhance the yield of propylene from catalytic cracking of vacuum gas oil (VGO). The catalytic performance of the additive was assessed using a commercial equilibrium USY FCC catalyst (E-Cat) in a fixed-bed micro-activity test unit (MAT) at 520?°C and various catalyst/oil ratios. MCM-41, ZSM-5 and two ZSM-5/MCM-41 composites were systematically characterized by complementary techniques such as XRD, BET, FTIR and SEM. The characterization results showed that the composites contained secondary building unit with different textural properties compared to pure ZSM-5 and MCM-41. MAT results showed that the VGO cracking activity of E-Cat did not decrease by using these additives. The highest propylene yield of 12.2 wt% was achieved over steamed ZSM-5/MCM-41 composite additive (ZM13) compared with 8.6 wt% over conventional ZSM-5 additive at similar gasoline yield penalty. The enhanced production of propylene over composite additive was attributed to its mesopores that suppressed secondary and hydrogen transfer reactions and offered easier transport and accessibility to active sites. Gasoline quality was improved by the use of all additives except MCM-41, as octane rating increased by 6?C12 numbers.     

WO3-ZSM-5/MCM-41催化剂的合成 及其催化氧化脱硫研究

以氢氧化钠溶液处理微孔沸石ZSM-5来提供硅铝源,合成了ZSM-5/MCM-41复合结构型分子筛。采用XRD、N2吸附脱附、TEM等方法对其进行了表征,考察了其水热稳定性。实验结果表明,碱处理合成的ZSM-5/MCM-41同时具有微孔孔道和介孔孔道结构,并具有优于介孔MCM-41分子筛的水热稳定性。以ZSM-5/MCM-41为载体负载三氧化钨后应用于噻吩/正辛烷模拟油体系,双氧水为氧化剂,催化氧化脱硫,WO3-ZSM-5/MCM-41（三氧化钨质量分数为10%）表现出良好的催化性能,脱硫率可达到93.6%。     

Fabrication and catalytic performance of meso-ZSM-5 zeolite encapsulated ferric oxide nanoparticles for phenol hydroxylation

An encapsulation-structured Fe₂O₃@meso-ZSM-5 (Fe@MZ5) was fabricated by confining Fe₂O₃ nanoparticles (ca. 4 nm) within the ordered mesopores of hierarchical ZSM-5 zeolite (meso-ZSM-5), with ferric oleate and amphiphilic organosilane as the iron source and meso-porogen, respectively. For comparison, catalysts with Fe₂O₃ (ca. 12 nm) encapsulated in intra-crystal holes of meso-ZSM-5 and with MCM-41 or ZSM-5 phase as the shell were also prepared via sequential desilication and recrystallization at different pH values and temperatures. Catalytic phenol hydroxylation performance of the as-prepared catalysts using H₂O₂ as oxidant was compared. Among the encapsulation-structured catalysts, Fe@MZ5 showed the highest phenol conversion and hydroquinone selectivity, which were enhanced by two times compared to the Fe-oxide impregnated ZSM-5 (Fe/Z5). Moreover, the Fe-leaching amount of Fe@MZ5 was only 3% of that for Fe/Z5. The influence of reaction parameters, reusability, and ·OH scavenging ability of the catalysts were also investigated. Based on the above results, the structure-performance relationship of these new catalysts was preliminarily described.     

Exploring suitable ZSM-5/MCM-41 zeolites for catalytic cracking of n-dodecane: Effect of initial particle size and Si/Al ratio

In this study, various ZSM-5/MCM-41 micro/mesoporous zeolite composites have been prepared by alkalidesilication and surfactant-directed recrystallization of ZSM-5. The effects of particle size and Si/Al ratio of initial ZSM-5 zeolites on the structure and catalytic performance of ZSM-5/MCM-41 composites are studied. The results of XRD, TEM N₂-adsorption-desorption, NH₃-TPD and in situ FT-IR revealed that ordered hexagonal MCM-41 mesopores with 3-4 nm pore size were formed around ZSM-5 crystals, and the specific surface area and mesopore volume of composites increased with increasing the Si/Al ratio of initial ZSM-5. Catalytic cracking of n-dodecane (550 ℃, 4 MPa) showed that the ZSM-5/MCM-41 composites obtained from the high Si/Al ratio and nano-sized initial ZSM-5 zeolites exhibited superior catalytic performance, with the improvement higher than 87% in the catalytic activities and 21% in the deactivation rate compared with untreated zeolites. This could be ascribed to their suitable pore structure, which enhanced the diffusion of reactant molecules in pores of catalysts.     

Selective catalytic reduction of nitric oxide with ammonia on Fe-ZSM-5 catalysts prepared by different methods

Fe-ZSM-5 catalysts, prepared by different methods, have been characterized by TPR and XRD and tested in the NO-SCR by NH_3. The sublimation method leads to the most active catalysts. Nevertheless the preparation starting from Fe(acac)₃, which is a preparation easy to implement from an industrial point of view, seems to be a very attractive alternative way.On the most active catalyst, Fe(0.83)_subZSM-5, prepared starting from FeCl₃, a study of the mechanism was undertaken. In the initial step of the SCR reaction, the oxidation of NO in NO₂, the re-oxidation of Fe^II species in the active iron oxo species is the slow phase.     

Selective Catalytic Reduction of NO with NH3 over Fe-ZSM-5 Catalysts Prepared by Sublimation of FeCl3 at Different Temperatures

Fe-ZSM-5 catalysts were prepared by subliming FeCl₃ into H-ZSM-5. The method used allowed Fe-ZSM-5 catalyst preparation by FeCl₃ exchange at a desired sublimation temperature and was found to be more precise. The sublimation of FeCl₃ into H-ZSM-5 was carried out at 320 and 700 °C. Fe-ZSM-5 prepared by sublimation of FeCl₃ at 320 °C followed by rapid heating to 700 °C and the catalyst prepared by subliming FeCl₃ at 700 °C were found to be more active for NO reduction with NH₃ in the presence of simulated exhaust gases containing water vapor than catalysts prepared by subliming FeCl₃ at 320 °C. To determine the active sites, the catalysts were characterized by H₂-TPR, in situ DRIFTS of NO adsorption, NH₃-TPD, XRD and chemical analysis methods. The observed NO conversion differences in selective catalytic reduction using NH₃ could be correlated to the iron cation species present at different locations determined from diffuse reflectance infrared spectroscopy. Enhanced NO reduction activity was obtained when positions in Fe-ZSM-5, corresponding to Fe²⁺(NO) band at 1877 cm^-1 in DRIFTS, were preferentially occupied.     

Hydroxylation of phenol with H2O2 over transition metal containing nano-sized hollow core mesoporous shell carbon catalyst

The catalytic performance of transition metal (Fe²⁺ or Cu²⁺) containing nano-sized hol low core mesoporous shell carbon (HCMSC) heterogeneous catalysts for the hydroxylation of phenol with hydrogen peroxide (H₂O₂) in water was investigated in a batch reactor. The metal-containing HCMSC catalyst showed higher activity than the same metal ion-exchanged zeolites. The nature of the metal and its content in the HCMSC had remarkable influence on the reaction results under the typical reaction conditions (PhOH/H₂O₂=3, reaction temperature=60 ‡C). Fe²⁺ containing HCMSC catalyst showed high catalytic activity with phenol conversion of 29%, selectivity to catechol (CAT) and hydroquinone (HQ) about 85%, H₂O₂ effective conversion about 70% and selectivity to benzoquinone (BQ) below 1% in the batch system.     

Noble Metal (Pt, Rh, Pd) Promoted Fe-ZSM-5 for Selective Catalytic Oxidation of Ammonia to N2 at Low Temperatures

We have reported previously the excellent performance of Fe-exchanged ZSM-5 for selective catalytic oxidation (SCO) of ammonia to nitrogen at high temperatures (e.g., 400-500 °C). The present work indicates that the reaction temperature can be decreased to 250-350 °C when a small amount of noble metal (Pt, Rh or Pd) is added (by both doping and ion exchange) to the Fe-ZSM-5. The SCO activity follows the order: Pt/Fe-ZSM-5 > Rh/Fe-ZSM-5 > Pd/Fe-ZSM-5. The noble metal promoted Fe-ZSM-5 catalysts also show higher activity for NH₃ oxidation than Ce-exchanged Fe-ZSM-5 at low temperatures. On the Pt promoted Fe-ZSM-5, near 100% of NH₃ conversion is obtained at 250 °C at a high space velocity (GHSV = 2.3 × 10⁵ h^-1) and nitrogen is the main product. The presence of H₂O and SO₂ decreases the SCO performance only slightly. This catalyst is a good candidate for solving the ammonia slip problem that plagues the selective catalytic reduction (SCR) of NO with ammonia in power plants.     

Catalytic activity of mesoporous catalysts in Friedel–Crafts benzylation of benzene

Different samples of metal-incorporated MCM-41 were prepared and used as catalysts in Friedel–Craft’s benzylation of benzene. The catalytic performance was evaluated by off-line GC analysis. Fe-MCM-41 exhibited excellent activity, the sample with Si/Fe ratio = 10 showed 90% conversion with 95% selectivity towards diphenylmethane within a few minutes. Generally, the activity per Fe-site was an order of magnitude higher for the samples containing a combination of Fe₂O₃ nano-particles and isolated Fe³⁺ sites. A synergy of two catalytic centers (particles and isolated sites) is proposed to explain the high performance of the highly loaded samples. The catalytic performance of Fe-MCM-41 was superior to other metal-containing MCM-41 (e.g. Ga, Sn, and Ti) catalysts, or other Fe-containing mesoporous materials (e.g. Fe-HMS).     

微孔-介孔分子筛负载氧化钴的苯催化完全氧化性能

用水热合成法合成了微孔-介孔分子筛MSZ,采用等体积浸渍法制备了Co_3O_4/微孔-介孔分子筛催化剂。用X射线衍射技术对材料进行表征,考察微孔-介孔分子筛的水热稳定性和催化剂对苯的催化完全氧化性能。研究发现,微孔-介孔分子筛水热稳定性较好,负载质量分数为35%Co_3O_4时,催化剂活性较高,活性组分晶粒的完整性和分散度是影响催化剂活性的重要因素,35%Co_3O_4/MSZ的活性高于35%Co_3O_4/MCM-41和35%Co_3O_4/ZSM-5。     

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.     

Selective ion-exchange in MAPO-36 and its application in toluene disproportionation

MAPO-36 was synthesized hydrothermally by isomorphic substitution of Mg²⁺ in the framework of AlPO-36 and ion-exchanged with Fe³⁺, Zn²⁺, La³⁺ and Ce³⁺ by wet method. The materials were characterized by XRD, TGA, TPD (ammonia) and SEM-EDX. XRD revealed absence of structural degradation after ion-exchange. TPD (ammonia) showed selective ion-exchange of strong acid sites in ion-exchanged MAPO-36. The weight loss around 550 °C in TGA for Fe, La and CeMAPO-36 suggested conversion of M(OH)₂⁺ to MO⁺. Toluene disproportionation was carried over all catalysts in which diphenyl methane derivative was suggested to be the principle intermediate in the formation of p-xylene and other products. The time on stream study showed exclusive formation of p-xylene after 6 h.     

Iron exchanged ZSM-5 and Y zeolites calcined at different temperatures: activity in N2O decomposition

ZSM-5 and Y zeolites were modified with iron by an ion-exchange method and then calcined at 773, 873, 973 and 1,073 K. The obtained materials were characterized with respect to textural parameters (low-temperature N₂ sorption), structure (X-ray diffraction, UV–vis–DRS), redox properties (H₂-temperature programmed desorption, TPD) and surface acidity (NH₃-TPD). The obtained results have shown that the structure of zeolites influenced form, aggregation and content of the introduced iron species. In case of the FAU type structure characterized by wide pores (max. ring size, T-atoms—12) mainly iron in form of mononuclear Fe³⁺ cations and Fe _x ³⁺ O_y oligonuclear clustered species was found. On the other hand for the MFI type structure characterized by smaller pores (max. ring size, T-atoms—10) significant contribution of iron in the form of bulky Fe₂O₃ clusters located possibly on the outer surface of ZSM-5 was detected. Such significant differences in distribution of iron species is probably related to various mobility of iron species in the pore systems of both zeolites. The obtained materials were tested as catalysts in the process of N₂O decomposition. Calcination of zeolites at different temperatures influenced neither the properties nor the activity of the obtained catalysts.     

Pt-loaded P-MCM-41 as a novel bifunctional catalyst for catalytic combustion of trichloroethylene

Pt-loaded P-MCM-41 catalysts with different Si/P ratio were prepared and used as novel bifunctional catalysts for catalytic combustion of trichloroethylene (TCE). Acidic materials, ZSM-5, P-SiO₂ and Al₂O₃ as supports in Pt-loaded catalysts were also studied for comparison. The high activity for TCE conversion and low selectivity to tetrachloroethylene were observed on Pt/P-MCM-41 catalysts, indicating that phosphorus modified MCM-41 with an amount of weak Brønsted acid sites, in combination with Pt, was effective to form a bifunctional catalyst.     

Oxidative dehydrogenation of n-butane over bimetallic mesoporous and microporous zeolites with CO2 as mild oxidant

Oxidative dehydrogenation of n-butane was tested using carbon dioxide as a mild oxidant over bimetallic Cr–V supported catalysts (MCM-41, ZSM-5, MCM-22 and mesoZSM-5). The textural properties of the catalysts were measured by means of XRD, N₂ adsorption, SEM-EDX, Raman, H₂-TPR, pyridine FT-IR, NH₃ and CO₂-TPD techniques. The metal content of Cr and V was maintained around 1.2 and 2.8 wt% for the catalytic test in packed bed reactor at different temperatures (525–600 °C) for 180 min. 1.2Cr2.8 V/MCM-41 and 1.2Cr2.8 V/ZSM-5 exhibited maximum conversion of 14 and 13.1 %, respectively at 10 min and 600 °C. Significantly, high butenes selectivity was observed over MCM-41 (86.27 %) than ZSM-5 support (58.1 %). The mesoporosity in ZSM-5 had a negative impact on conversion level (7.1 %) but improved the butenes selectivity slightly. 1.2Cr2.8 V/M-22 showed the highest cracking ability leading to overall reduced butenes selectivity (57.9 %). The study shows that over all catalysts, n-butane conversion is independent of CO₂ conversion. 1.2Cr2.8 V/M-22 showed highest CO₂ conversion in the range 2.35–2.2 % between 525 and 550 °C. The apparent activation energies of dehydrogenation and cracking reaction over the four catalysts were evaluated. The ratio of conversion to coke weight per cent over the four catalysts are observed in the following order: 1.2Cr2.8 V/M-41 > 1.2Cr2.8 V/Z-5 > 1.2Cr2.8 V/mesoZ-5 > 1.2Cr2.8 V/M-22.     

Role of acidity of catalysts on methane combustion over Pd/ZSM-5

Palladium-based catalysts were prepared by the impregnation (I) and ion-exchange method (E) with ZSM-5 and γ-Al₂O₃ as support respectively. The high activity of Pd/ZSM-5(I) and Pd-ZSM-5(E) catalysts for methane combustion was observed. The order of activity is consistent with Brønsted acidity of catalysts: Pd/ZSM-5(I) > Pd-ZSM-5(E) > Pd/Al₂O₃. It is shown by FT-IR that methane adsorbs on acidic bridging hydroxyl groups of ZSM-5-supported Pd catalysts. Symmetric v₁ C–H stretching vibrations of methane shift to low frequency due to the interaction between methane molecules and Brønsted acid sites or Pd²⁺, indicating that methane molecules can be activated.     

Mesoporous Fe-containing ZSM-5 zeolite single crystal catalysts for selective catalytic reduction of nitric oxide by ammonia

Mesoporous and conventional Fe-containing ZSM-5 catalysts (0.5–8 wt% Fe) were prepared using a simple impregnation method and tested in NO selective catalytic reduction (SCR) with NH₃. It was found that mesoporous Fe-ZSM-5 catalysts exhibit higher SCR activities than comparable conventional catalysts. Furthermore, conventional Fe-ZSM-5 catalysts have maximum activity at ~2.5 wt% Fe while for the mesoporous system, optimal NO conversion is obtained for the catalysts with ~6 wt % Fe.