Selective Dealumination of ZSM-5 by Hydrothermal Treatment

We studied the factors affecting the framework aluminium distribution in the ZSM-5 structure by hydrothermal treatment under different conditions. (27)AlMASNMR, XPS and chemical analysis revealed that with steaming at lower water vapor pressure, the framework aluminium located at the external surface is less stable. Steaming at higher water vapor pressure is beneficial in removing the framework Al in HZSM-5, and especially helpful in removing that located at the internal surface of HZSM-5. By changing steaming conditions, one may control the framework aluminium distribution in the HZSM-5 structure.

Mechanism of Dealumination of NaY Zeolite with Oxalic Acid

Dealuminated Y zeolite with high crystallinity is obtained from NaY zeolite by treatment with oxalic acid in a buffering system. The effect of dealumination conditions on the degree of dealumination and the crystallinity of the reformed zeolite is discussed. A mechanism for the reaction is proposed.

^(29)Si MAS-NMR STUDIES ON DEALUMINATION OF MORDENITE

A series of different H-mordenites from acid leaching and steam calcination have beenmeasured with 29Si NMR. Through analysis of these solid-state 29Si NMR spectra, theresults related to dealumination process of mordenite are obtained. It is shown that mor-denite is combined by four kinds of non-equivalent Si （or Al） via oxygen bridges. The deal-umination order is T（1）, T（2）, T（4） and T（3）. The dealuminated amount in the non-equivalentsites during different dealumination processes has also been discussed in detail.

Surface dealuminated Beta zeolites supported WO3 catalyst and its catalytic performance in tetralin hydrocracking

In this study,selective dealumination of Beta zeolites was performed through partially removing the templating agent in Beta zeolites by calcination and then removing the aluminum on the external surface of Beta zeolites with acid treatment.Hydrocracking catalysts were prepared by loading WO_(3)onto these dealuminated Beta zeolites.It was shown that the surface SiO_(2)/Al_(2)O_(3)of selectively dealuminated Beta zeolites was higher than that of conventionally dealuminated samples for the same bulk SiO_(2)/Al_(2)O_(3),and the hydrogenation activity of the catalyst of the selectively dealuminated Beta zeolites was lower than that of conventionally dealuminated Beta zeolites.The experimental results for tetralin hydrocracking to BTX showed that the catalysts based on the selectively dealuminated Beta zeolites had higher BTX selectivity and lower coke formation rate than that the catalysts based on the conventionally dealuminated Beta zeolites.

Dealuminated ZSM-5 Zeolite Catalyst for Ethylene Oligomerization to Liquid Fuels

Ethylene oligomerization using ZSM-5 zeolite was investigated to study the role of Bronsted acid sites in the formation of higher hydrocarbons. The oligomerization of olefins, dependent on the acidity of ZSM-5 zeolite, is an important step in the conversion of natural gas to liquid fuels. The framework Si/Al ratio reflects the number of potential acid sites and the acid strength of the ZSM-5 catalyst. ZSM-5 with the mole ratio SiO2/Al2O3 equal to 30 was dealuminated for different periods of time according to the acidic ion-exchange method to produce ZSM-5 with various Si/Al ratios. The FT-IR analysis revealed that the integrated framework aluminum band, non-framework aluminum band, and silanol groups areas of the ZSM-5 zeolites decreased after being dealuminated. The performance of the dealuminated zeolite was tested for ethylene oligomerization. The results demonstrated that the dealumination of ZSM-5 led to higher ethylene conversion, but the gasoline selectivity was reduced compared to the performance of a ZSM-5 zeolite. The characterization results revealed the amount of aluminum in the zeolitic framework, the crystallinity of the ZSM-5 zeolite, and the Si/Al ratio affected the formation of Bronsted acid sites. The number of the Bronsted acid sites on the catalyst active sites is important in the olefin conversion to liquid hydrocarbons.

Hydrothermal Chemistry Involved in Developing Practical Y Type Zeolite Catalysts

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Study on Modified Y Zeolites and Their Behaviors in Selective Adsorptive Desulfurization of FCC Gasoline (Ⅰ)

NaY zeolite was modified through dealumination with oxalic acid,and the HY zeolite was obtained by calcination of the modified NaY zeolite.The zeolite molding process was carried out at ambient temperature(25℃),and the influence of solid/fuel mass ratio and adsorptive desulfurization time on the HY zeolite were investigated through tests on static selective adsorptive desulfurization of FCC gasoline containing organic sulfur compounds(with a S content=135 ppm).The sulfur content and sulphide types in the FCC gasoline were analyzed by a GC 2010 sulfur analyzer and a GC-SCD chromatograph.The test results showed that the molded HY zeolite was better than the unmolded HY zeolite.At a static adsorptive desulfurization time on the molded HY zeolite equating to 6 hours,a solid/fuel mass ratio of 1:3,the sulfur content of FCC gasoline was decreased to 30 ppm,and the desulfurization rate was equal to 78%.When the breakthrough point of the molded HY was equal to 50 ppm,the molded HY zeolite was capable of adsorbing 4.86 mg of sulfur per gram of adsorbent.And the regeneration rate of molded HY zeolite was equal to 98%.

A Selective Octane-Enhancing FCC Catalyst Using ZRP Zeolite as an Active Component

A hetero-crystalline seeding method to prepare a unique MFI type zeolite with mesopores of ca. 4 nm diameter designated as the ZRP zeolite, which possesses high stability and selectivity and is used as component of FCC catalysts to produce high-octane gasoline and light olefins, was developed. With the DOCR and DOCP catalysts containing the ZRP zeolite modified by phosphorus-incorporation as the octaneenhancing catalysts, the commercial trial was carried out in a 0.8Mt/a RFCC unit with a feedstock composed of Daqing atmospheric residue. As compared to the base catalyst, the LPG+gasoline+LCO product yield obtained from this catalyst was increased by 0.53m%. Meanwhile, the RON and MON of gasoline was increased by 1.4 and 2.4 units, respectively. The higher increment of MON is attributable to the higher isoparaffines content in gasoline. This result indicates that the ZRP zeolite possesses higher isomerization selectivity.

Alkylation of o-Xylene with Styrene over Modified Mordenite for Environmentally Friendly Synthesis of PXE

Effects of hydrochloride acid dealumination of mordenite(MOR) catalysts for the synthesis of 1-phenyl-1-xylyl ethane(PXE) were investigated. The structure and acidity of catalysts were characterized by XRD, BET, XRF, FT-IR, 27Al NMR and NH3-TPD techniques. The catalytic performance of the acid-treated MOR zeolites was studied through using the alkylation of o-xylene with styrene. The test results showed that the strength of remaining Br?nsted acid sites increased despite the reduction of total number of acid sites after dealumination, and the micropores of HMOR were slightly enlarged coupled with the formation of secondary mesopores. Additionally, the modified HMOR zeolites showed longer catalyst life with the styrene conversion rate retained. Among the catalysts employed in this study, the modified mordenite that was dealuminated by HCl(2 mol/L) could be used repeatedly without significant loss of activity and selectivity during six catalytic runs, which have been ascribed to its specific acidity and structural properties.

Synthesis of Zeolite X from Locally Sourced Kaolin Clay from Kono-Boue and Chokocho, Rivers State, Nigeria

This work describes the development of a process to produce zeolite X from mined kaolin clay from Kono-Boue and Chokocho, Rivers State, Nigeria. The procedures involved the beneficiation of the raw kaolin and calcinations at 850°C, to transform the kaolin to a more reactive metakaolin. Afterwards, the extremely reactive metakaolin was purge with sulphuric acid to obtain the much needed silica-alumina ratio for zeolite X synthesis. An alkaline fusion stage was then carried out to transform the metakaolin into zeolite by mixing with aqueous NaOH to form gel then allowed to stay for a duration of seven days at room temperature. The samples were then charged into a propylene container and placed in an oven at a temperature of 100°C for the reaction to take place for 6 h. Identification of the crystalline phases by X-ray Diffraction (XRD), chemical/elemental compositions by X-ray Fluorescence (XRF)/Energy Dispersive Spectroscopic analyses (EDS), surface morphology by Scanning Electron Microscopy (SEM) and molecular vibration of units by Fourier Transform Infrared Spectrophotometry (FT-IR) were done. The results showed that the zeolite synthesized from Chokocho kaolin (CK) was more crystalline/larger with sharper peaks on both XRD and FTIR than that from Kono-Boue. This was also supported by slightly rougher surface morphology of CK over KK on SEM. XRF Si:Al ratios of 10.73 and 14.36 were obtained for KK and CK respectively. EDS results supported the XRF ratios. Sharper zeolitic characteristic O-H stretching bands at 3488 and 3755 cm-1 were recorded for CK than KK. However, both results showed that zeolite X have been produced from both Kono-Boue and Chokocho kaolin clays respectively.

Investigation of Ce/BEA as a passive NO_(x)adsorber:2.Hydrothermal aging deactivation mechanism

Ce/BEA has the potential to be applied as a novel passive NO_(x)absorber(PNA)in the after-treatment of vehicles due to its considerable NO_(x)storage capacity.However,as a vehicle exhaust after-treatment material,it must withstand the test of long-term hydrothermal aging.This work examined the deactivation mechanism of Ce/BEA during hydrothermal aging.3.0 wt%Ce/BEA was prepared using the ionexchange method,and then subjected to hydrothermal treatment at 650℃with 10%H_(2)O for 1-12 h to obtain samples with different aging extent.For comparison,the H-BEA support was aged under the same conditions.Brunauer-Emmett-Teller(BET)method,X-ray diffraction(XRD),NH_(3)temperature programmed reduction(NH_(3)-TPD),^(27)Al MAS nuclear magnetic resonance(^(27)Al MAS NMR),H_(2)temperature programmed reduction(H_(2)-TPR),and high resolution-transmission electron microscopy(HR-TEM)were performed to characterize the changes in PNA performance,structure,Ce species,and acidity.The HR-TEM and H_(2)-TPR results show that CeO_(x)particles appear after hydrothermal aging,which results from the detachment and aggregation of active Ce species.Based on the^(27)Al MAS NMR results,we conclude that BEA zeolite dealumination leads to the loss of acidic sites and the transformation of active Ce species on the acidic sites into the less active CeO_(x).This is the primary reason for the hydrothermal aging deactivation of Ce/BEA.

Alkaline modification of ZSM-5 catalysts for methanol aromatization： The effect of the alkaline concentration

The effects of alkaline treatment on the physical properties of ZSM-5 catalysts and on their activities for methanol to aromatics conversion have been investigated. A mild alkaline treatment （0.2 and 0.3 mol/L NaOH） created mesopores in the parent zeolite with no obvious effect on acidity. The presence of mesopores gives the catalyst a longer lifetime and higher selectivity for aromatics. Treatment with 0.4 mol/L NaOH decreased the number of Bronsted acid sites due to dealumination and desilication, which resulted in a lower deactivation rate. In addition, more mesopores were produced than with the mild alkaline treatment. As a result, the lifetime of the sample treated with 0.4 mol/L NaOH was almost five times that of the parent ZSM-5. Treatment with a higher alkaline concentration （0.5 mol/L） greatly reduced the number of Bronsted acid sites and the number ofmicropores resulting in incomplete methanol conversion. When the alkalinetreated catalysts were washed with acid, some of the porosity was restored and a slight increase in selectivity for aromatics was obtained.

Using ultrasound to improve the sequential post-synthesis modification method for making mesoporous Y zeolites

Mesoporous Y zeolites were prepared by the sequential chemical dealumination(using chelating agents such as ethylenediaminetetraacetic acid,H EDTA,and citric acid aqueous solutions)and alkaline desilication(using sodium hydroxide,NaOH,aqueous solutions)treatments.Specifically,the ultrasound-assisted alkaline treatment(i.e.,ultrasonic treatment)was proposed as the alternative to conventional alkaline treatments which are performed under hydrothermal conditions.In comparison with the hydrothermal alkaline treatment,the ultrasonic treatment showed the comparatively enhanced efficiency(with the reduced treatment time,i.e.,5 min vs.30 min,all with 0.2 mol·L NaOH at 65°C)in treating the dealuminated Y zeolites for creating mesoporosity.For example,after the treatment of a dealuminated zeolite Y(using 0.1 mol·L H EDTA at 100°C for 6 h),the ultrasonic treatment produced the mesoporous zeolite Y with the specific external surface area()of 160 m·g and mesopore volume()of 0.22 cm·g,being slightly higher than that by the conventional method(i.e.,=128 m·g and=0.19 cm·g).The acidic property and catalytic activity(in catalytic cracking of-octane)of mesoporous Y zeolites obtained by the two methods were comparable.The ultrasonic desilication treatment was found to be generic,also being effective to treat the dealuminated Y zeolites by citric acid.Additionally,the first step of chemical dealumination treatment was crucial to enable the effective creation of mesopores in the parent Y zeolite(with a silicon-to-aluminium ratio,Si/Al=2.6)regardless of the subsequent alkaline desilication treatment(i.e.,ultrasonic or hydrothermal).Therefore,appropriate selection of the condition of the chemical dealumination treatment based on the property of parent zeolites,such as Si/Al ratio and crystallinity,is important for making mesoporous zeolites effectively.

A theoretical study of hydrothermal stability of P-modified ZSM-5 zeolites

Density functional theory was employed to study the hydrothermal stability of P-modified ZSM-5 zeolites using cluster models. The calculations of hydrolysis energies indicated that the introduction of phos-phorus increases the hydrothermal stability of ZSM-5 zeolites. The initial paths of dealumination were studied with explicit water molecules. It was found that the framework Al-O coordination bond can be replaced by coodination bonds between water molecules and the aluminium. One to three water molecules can form coordination bonds with framework Al and release energies. The P-modification restrain the dealumination. The calculated 27Al NMR chemical shifts for the obtained structures are consistent with the experimental measurements.