Creating mesopores in ZSM-48 zeolite by alkali treatment: Enhanced catalyst for hydroisomerization of hexadecane

ZSM-48 zeolites with various Si/Al ratios were hydrothermally synthesized in the H;N（CH;）;NH;（HDA）-containing media. The obtained samples were highly crystallized with minor mixed phases as evidenced by X-ray powder diffraction（XRD）. The alkaline treated ZSM-48 zeolites maintained its structure under different concentrations of Na OH aqueous solution. Micropores remained unchanged while mesopores with wide pore size distribution formed after the alkaline treatment. The surface area increased from 228 to 288 m;/g. The Br?nsted acid sites had little alteration while an obvious increase of Lewis acid sites was observed. The hydroisomerization of hexadecane was performed as the model reaction to test the effects of the alkali treatment. The conversion of hexadecane had almost no change, which was attributed to the preservation of the Br?nsted acid sites. While high selectivity to iso-hexadecane with an improved iso to normal ratio of alkanes was due to the mesopore formation and improved diffusivity.

Removal of Organochlorine from Model Oil Using Mg-Modified ZSM-5 Zeolite:Dechlorination Performance,Regeneration,and Thermodynamics

Various metal-modified ZSM-5 zeolite adsorbents prepared by the impregnation method were applied to the removal of organic chlorides from model naphtha.The adsorption performance and regeneration stability were investigated by static adsorption experiments.The morphologies,structural features,and physicochemical properties of the adsorbents were characterized by X-ray diffraction,Brunauer-Emmett-Teller analysis,NH3 temperature-programmed desorption,scanning electron microscopy,transmission electron microscopy,and pyridine adsorption infrared spectroscopy.The Mg/ZSM-5 zeolite adsorbent possessed a relatively high specific surface area and good metal dispersion and exhibited the best dechlorination and regeneration performance.The characterization results revealed that introduction of the metal exerted a significant influence on the acidic properties of the catalyst surface.A decrease in the ratio of Brønsted acidic sites to Lewis acidic sites and an increase in the amount of moderately acidic sites were confirmed to be responsible for the excellent adsorption performance of the Mg-modified ZSM-5 zeolite.Furthermore,the Langmuir adsorption isotherm model was applied to study the adsorption equilibrium and thermodynamics of the Mg/ZSM-5 adsorbent under mild conditions.The results revealed that the removal of 1,2-dichloroethane by the Mg/ZSM-5 adsorbent was endothermic,spontaneous,disordered,and primarily involved physical adsorption.

Synthesis and characterization of an unusual snowflake-shaped ZSM-5 zeolite with high catalytic performance in the methanol to olefin reaction

The ZSM-5 zeolite with an unusual snowflake-shaped morphology was hydrothermally synthesized for the first time,and compared with common ellipsoidal and boat-like shaped samples.These samples were characterized by N2 adsorption-desorption,X-ray fluorescence spectroscopy,scanning electron microscopy,X-ray diffraction,magic angle spinning nuclear magnetic resonance,temperature-programmed desorption of ammonia,and infrared spectroscopy of pyridine adsorption.The results suggest that the BET surface area and SiO2/Al2O3 ratio of these samples are similar,while the snowflake-shaped ZSM-5 zeolite possesses more of the（101） face,and distortion,dislocation,and asymmetry in the framework,resulting in a larger number of acid sites than the conventional samples.Catalysts for the methanol to olefin（MTO） reaction were prepared by loading Ca on the samples.The snowflake-shaped Ca/ZSM-5 zeolite exhibited excellent selectivity for total light olefin（72%） and propene（39%） in MTO.The catalytic performance influenced by the morphology can be mainly attributed to the snowflake-shaped ZSM-5 zeolite possessing distortion,dislocation,and asymmetry in the framework,and lower diffusion limitation than the conventional samples.

Alkali-metal-modified ZSM-5 zeolites for improvement of catalytic dehydration of lactic acid to acrylic acid

Various ZSM-5 zeolites modified with alkali metals （Li, Na, K, Rb, and Cs） were prepared using ion exchange. The catalysts were used to enhance the catalytic dehydration of lactic acid （LA） to acrylic acid （AA）. The effects of cationic species on the structures and surface acid-base distributions of the ZSM-5 zeolites were investigated. The important factors that affect the catalytic performance were also identified. The modified ZSM-5 catalysts were characterized using X-ray diffraction, tempera- ture-programmed desorptions of NH3 and CO2, pyridine adsorption spectroscopy, and N2 adsorption to determine the crystal phase structures, surface acidities and basicities, nature of acid sites, specific surface areas, and pore volumes. The results show that the acid-base sites that are adjusted by alkali-metal species, particularly weak acid-base sites, are mainly responsible for the formation of AA. The KZSM-5 catalyst, in particular, significantly improved LA conversion and AA selectivity because of the synergistic effect of weak acid-base sites. The reaction was conducted at different reaction temperatures and liquid hourly space velocities （LHSVs） to understand the catalyst selectivity for AA and trends in byproduct formation. Approximately 98% LA conversion and 77% AA selectivity were achieved using the KZSM-5 catalyst under the optimum conditions （40 wt% LA aqueous solution, 365 ℃, and LHSV 2 h-1）.

Hydroisomerization performance of platinum supported on ZSM-22/ZSM-23 intergrowth zeolite catalyst

Hydroisomerization catalysts Pt/ZSM-22, Pt/ZSM-23, and Pt/ZSM-22/ZSM-23 were prepared by supporting Pt on ZSM-22, ZSM-23, and intergrowth zeolite ZSM-22/ZSM-23, respectively. The typical physicochemical properties of these catalysts were characterized by X-Ray Diffraction （XRD）, N2 absorption-desorption, Pyridine-Fourier Transform Infrared （Py-FTIR）, Transmission Electron Microscopy （TEM）, X-Ray Fluorescence （XRF）, Scanning Electron Microscopy （SEM） and NH3- Temperature Programmed Desorption （NH3-TPD）, and the performance of these catalysts in n-dodecane hydroisomerization was evaluated in a continuous down-flow fixed bed with a stainless steel tubular reactor. The characterization results indicated that the intergrowth zeolite ZSM-22/ZSM-23 possessed the dual structure of ZSM-22 and ZSM-23, and the catalyst Pt/ZSM-22/ZSM-23 had similar pores and weak acidity to Pt/ZSM-22 and Pt/ZSM-23 catalysts. Moreover, Pt/ZSM-22/ZSM-23 catalyst showed a high selectivity in hydroisomerization of long chain n-alkanes to mono-branched isomers. The evaluation results for n-dodecane hydroisomerization indicated that the activity of Pt/ZSM-22/ZSM-23 was the lowest, while the hydroisomerization selectivity was the highest among the three catalysts. The maximum yield of i-dodecane product was 68.3% over Pt/ZSM-22/ZSM-23 at 320 ℃.

Disproportionation of Toluene by Modified ZSM-5 Zeolite Catalysts with High Shape-selectivity Prepared Using Chemical Liquid Deposition with Tetraethyl Orthosilicate

Shape-selective catalysts for the disproportionation of toluene were prepared by the modification of the cylinder-shaped ZSM-5 zeolite extrudates with chemical liquid deposition with TEOS （tetraethyl orthosilicate）.Various parameters for preparing catalysts were changed to investigate the suitable conditions.The resulting cata-lysts were tested in a pressured fixed bed reactor and characterized by SEM （scanning electron microscopy）.The conversion of toluene and para-xylene selectivity were influenced remarkably by the n（SiO2）/n（Al2O3） ratio of ZSM-5 zeolite,the type and amount of deposition agent,acid and solvent used,and the time and cycle of deposition treatment.TEOS was proved to be a more efficient agent than the conventional polysiloxanes when the deposition amount was low.The catalyst prepared at the suitable conditions exhibited a high para-xylene selectivity of 91.1% with considerable high conversion of 25.6%.SEM analyses confirmed the formation of a layer of amorphous silica on the external surface of ZSM-5 zeolie crystals,which was responsible for the highly enhanced shape-selectivity.

Aromatization over nanosized Ga-containing ZSM-5 zeolites prepared by different methods:Effect of acidity of active Ga species on the catalytic performance

Nanosized Ga-containing ZSM-5 zeolites were prepared via isomorphous substitution and impregnation followed by characterized using various techniques. The catalytic performance of the zeolites for the aromatization of 1-hexene was investigated. The results indicate that isomorphous substitution promotes the incorporation of Ga heteroatoms into the framework along with the formation of extra-framework GaO;species（[GaO;]a） that have stronger interactions with the negative potential of the framework. In addition, based on the Py-IR results and catalytic performance, the [GaO;]aspecies with stronger Lewis acid sites produced a better synergism with moderate Br?nsted acid sites and thus improved the selectivity to aromatic compounds. However, the impregnation results in the formation of Ga;O;phase and small amounts of GaO;species that are mainly located on the external surface（[GaO;];）, which contribute to weaker Lewis acid sites due to weaker interactions with the zeolite framework. During 1-hexene aromatization, the nanosized Ga isomorphously substituted ZSM-5 zeolite samples（Gax-NZ5） exhibited better catalytic performance compared to the impregnated samples, and the highest aromatic yield（i.e.,65.4 wt%） was achieved over the Ga4.2-NZ5 sample, which contained with the highest Ga content.

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 ℃.

Experiment and Modeling of Pure and Binary Adsorption of n-Butane and Butene-1 on ZSM-5 Zeolites with Different Si/Al Ratios

Four ZSM-5 zeolite catalysts with different Si/Al ratios for the catalytic cracking of C4 fractions to produce ethylene and propylene were prepared in this study.First,the adsorption isotherms of pure n-butane and butene-1 and their mixtures on these catalysts at 300K and p=0—100kPa were measured using the intelligent gra- vimetric analyzer.The experimental results indicate that the presence of Al can significantly affect the adsorption of butene-1 than that of n-butane on ZSM-5 zeolites.Then,the double Langmuir(DL)model was applied to study the pure gas adsorption on ZSM-5 zeolites for pure n-butane and butene-1.By combining the DL model with the ideal adsorbed solution theory(IAST),the IAST-DL model was applied to model the butene-1(1)/n-butane(2)binary mixture adsorption on ZSM-5 zeolites with different Si/Al ratios.The calculated results are in good agreement with the experimental data,indicating that the IAST-DL model is effective for the present systems.Finally,the adsorp- tion over a wide range of variables was predicted at low pressure and 300K by the model proposed.It is found that the selectivity of butene-1 over n-butane increases linearly with the decrease of Si/Al ratio.A correlation between the selectivity and Si/Al ratio of the sample was proposed at 300K and p=0.08MPa.

Adsorption of Benzene and Propylene in Zeolite ZSM-5:Grand Canonical Monte Carlo Simulations

The adsorption behavior of benzene and propylene in zeolite ZSM-5 was studied by Grand Canonical Monte Carlo（GCMC） simulations. It could be found that benzene and propylene molecules showed different adsorption behavior in the zeolite cavities. The loadings of propylene were significantly larger than those of benzene at 100 kPa. From the figures of potential energy distribution, the potential energy of benzene/zeolite was more negative than that of propylene/zeolite, so benzene could be adsorbed more stably than propylene. When the temperature was in- creased from 298 to 443 K at 100 kPa, the loading ofpropylene was reduced from 99 to 82 molecules, whereas that of benzene changed little. When benzene and propylene were adsorbed in zeolite simultaneously, the competitive adsorption of them occurred; therefore, the potential energy distribution could be changed significantly. Besides, the adsorption isotherms of benzene and propylene in ZSM-5 at 298 and 443 K were simulated. The results exhibit that the different factors influenced the molecular adsorption at various temperatures and pressures, leading to the diffe- rent rules for the adsorption of benzene and propylene molecules in the zeolite. At a low pressure, the unfavorable energy of propylene/zeolite and the ＂commensurate freezing＂ phenomenon of benzene would make the loadings of itself higher than those of propylene. When pressure was higher than 5 kPa, the adsorption of benzene in ZSM-5 would nearly reach saturation.

A novel method for enhancing the stability of ZSM-5 zeolites used for catalytic cracking of LPG: Catalyst modification by dealumination and subsequent silicon loading

Composite structures of ZSM‐5 zeolites were prepared by the synthesis of mesopores and mi‐cropores using carbon nanotubes as a template. Dealumination of mesopores was performed selec‐tively using trichloroacetic acid, which could only diffuse into the mesopores and not the mi‐cropores owing to the size of the trichloroacetic acid molecules. Empty spaces are created in the catalyst as a result of removal of the Al atoms from the zeolite structure. If Si atoms fill the empty space, then the structure of the mesopores becomes similar to silicates, which do not have any cata‐lytic properties. Silicon containing solution was used to fill the empty spaces, and in doing so, a unique method was developed, by which silicon atoms can directly replace the extracted Al atoms from the mesopore structure. Therefore, by changing the geometry and properties of the mesopores and micropores, the amount of coke reduced from 14%for HZSM‐5 to 3%for the modified zeolite.

Rapid synthesis of ZSM-5 zeolite catalyst for amination of ethanolamine

ZSM-5 zeolite was rapidly synthesized in system containing ethylenediamine from the initial gel: (5?8) Na2O: 44 EDA:Al2O3:100 SiO2:4000 H2O. The crystals were lath-shaped. The effect of pretreatment and alkalinity on crystallinity was investigated. The pretreatment of silicate source can cut down the crystallization time. Tuning the system alkalinity and controlling crystallization time can ensure forming of pure crystal.

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 N_2-adsorption-desorption,NH_3-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.

Physicochemical Features of Phosphorus-Modified ZSM-5 Zeolite and Its Performance on Catalytic Pyrolysis to Produce Ethylene

The physicochemical features of phosphorus-modified ZSM-5 zeolites (SiO2/Al2O3 molar ratio is 25) were characterized by XRD(X-ray diffraction), BET(Brunauer, Emmett and Teller spcific surface area measurement), NH3-TPD(ammonia temperature-programmed desorption) and MASNMR(magic angle spinning nuclear magnetic resonance), and the performance on catalytic pyrolysis to produce ethylene was investigated with a light hydrocarbon fixed bed micro-reactor with n-octane as feed. The results show that the acid site density, acid intensity and hydrothermal stability of ZSM-5 zeolite were improved by phosphorus modification. When P2O5 content in ZSM-5 zeolite is higher than 2.5%, phosphorus modification can prevent ZSM-5 zeolite crystal structure transformation from orthorhombic to monoclinic. In addition, the dealumination of ZSM-5 zeolite framework was moderated by phosphorus modification under high temperature hydrothermal treatment. The results of n-octane pyrolysis on phosphorus-modified ZSM-5 zeolites show that ethylene yields of zeolites with different phosphorus content are almost the same under the same n-octane conversion. However, the modified zeolites with higher pyrolysis activity give lower yield of propene, butene and total olefin than lower pyrolysis activity under the same n-octane conversion.

Effects of Metal Oxide in ZSM-5 Zeolite on Its Catalytic Performance in FCC Process

Effects of metal oxide in ZSM-5 zeolite on its catalytic performance in fluid catalytic cracking reaction were studied via characterization by XRD and FT-IR spectroscopy using pyridine and collidine as molecular probes,and the modified ZSM-5 zeolite was evaluated in a micro reactor using standard light diesel fraction as the feedstock.Test results indicate that the metal species introduced into the ZSM-5 zeolite had led to the formation of Lewis acid centers.When the modified ZSM-5 zeolite with the metal species on its surface was used as the catalyst in FCC reaction,both the propylene yield and the propylene concentration in the liquefied petroleum gas increased,but in the meantime,more hydrogen and coke were formed at high conversion rate under the joint action of nonselective cracking of Lewis acid centers and dehydrogenation at metal centers on its outside surface.

Synthesis of ZSM-5 zeolite membranes without organic templates using a varying-concentration technique

Template-free nanosized ZSM-5 seeds with an average size of 15 nm were prepared from a synthesis solution with the composition 12Na2O∶100SiO2∶2Al2O3∶2500H2O. By the use of these seeds, thin ZSM-5 zeolite membranes were prepared on the outer surface of a porous α-alumina tube with a pore size of 2 μm in a gel system by varying-concentration synthesis with organic-free template. The first composition synthesis sol-gel was the same as seeds of molar composition and the second one was 12Na2O∶100SiO2∶2Al2O3∶5000H2O at 180 ℃ for 10 h, respectively. XRD shows that the film consists of well-crystallized ZSM-5 zeolite. SEM investigation indicats that the zeolite films on the supports are defect free and the film thickness is approximately 8 μm. The permeances for H2, N2, CH4 and CO2 are 8.94×10-7, 3.27×10-7, 3.9×10-7, 3.14×10-7 and 0.874×10-7 mol·m2·s-1·Pa-1, respectively. The ideal selectivity of membrane at room temperature for H2/CO2, H2/N2, H2/CH4 are 2.84, 2.73 and 2.29, respectively.

The Difference between ZSM-5 Zeolites Manufactured from Various Synthesis Systems and Their Catalytic Performances

ZSM-5 zeolites with similar St/Al ratio were synthesized successfully using various templates [n- butylamine （BTA）, tetrapropylammonium bromide （TPABr） and no template （NT）] under hydrothermal conditions, The samples were characterized by XRD, SEM, Py-IR and BET surface area measurements in order to understand the template eiTects and the differences between the ZSM-5 santples. The synthesis of ZSM-5 with organic templates was relatively easier than those with inorganic templates and withnut template. SEM results revealed that ZSM-5 synthesized with different templates had different morphologies in similar particle size. Toluene disproportiortation reaction was carried out over the catalyst samples to evaluate the catalytic properties. The results have shown that large crystals which have a correspondingly small external surface showed a high para-xylene selectivity, and the amount of C9^＋ and C5^＋ was much less than that obtained from zeolite with small crystals.

Effect of Steam Treatment on the Catalytic Performance of ZSM-5 in the Co-conversion of Methanol and n-Hexane to Aromatics

Steam pretreatment is a widely used method for modifying the acidity and structure of zeolites,thereby enhancing their catalytic properties.This study systematically investigated the effects of steam treatment on ZSM-5 zeolites at varying treatment temperatures and durations.The structural evolution of the catalysts was monitored using N2 adsorptiondesorption,X-ray diffraction,inductively coupled plasma optical emission spectroscopy,scanning electron microscopy,NH3 temperature-programmed desorption,in situ pyridine infrared spectroscopy,and thermogravimetric analysis.The characterization results revealed that mesopores were introduced into the ZSM-5 zeolite catalysts through dealumination induced using steam treatment at moderate temperatures(400 and 500℃).Moreover,compared with the parent catalyst,the steam-treated catalysts exhibited a lower amount of acid sites and relative crystallinity,while the n(Si)/n(Al)ratio increased.In the co-conversion of methanol and n-hexane in a fixed bed reactor at 400℃and 0.5 MPa(N2 atmosphere),with a weight hourly space velocity of 1 h−1 and a stoichiometric ratio of 1:1(CH3OH to n-hexane),the steam-treated catalysts displayed a prolonged catalyst lifetime.Particularly,the parent zeolite had a lifetime of 96 h,while the catalyst treated at 500℃for 12 h had a lifetime of up to 240 h.Additionally,the steam-treated catalysts maintained stable n-hexane conversion and improved aromatic selectivity.Notably,these treated catalysts exhibited a lower deactivation rate than the parent catalyst,and would be conducive to industrial scale-up production.

Synthesis and Characterization of ZSM-5/β Co-Crystalline Zeolite

ZSM-5/β co-crystalline zeolites with different content of ZSM-5 have beensynthesized by adding different amount of ZSM-5 to the synthetic system of β zeolite with NaAlO_2,silica sol as the source of aluminum and silica, respectively, and TEA^+ as the template undercontrolled condition of the synthesis. The ZSM-5/β co-crystalline zeolite was studied by XRD, SEM,BET and NH_3-TPD. The reaction activity of toluene alkylation was investigated with a mixture oftoluene-methanol as the feedstock in a pulse micro-reactor over the ZSM-5/β co-crystalline zeolite.It is found that ZSM-5/β co-crystalline zeolite has two kinds of zeolite structure including ZSM-5and β zeolite, not in the form of a physical mixture. The pore structure of ZSM-5/βco-crystalline zeolites is different from that for β zeolite, ZSM-5 and their physical mixture. Inaddition, the peaks of both high and low temperature desorption of ammonia over the ZSM-5/βco-crystalline zeolite shift 23℃ to lower temperatures and the acid amount of its strong acid is 3%more than the physical mixture. So the ZSM-5/β co-crystalline zeolite produces the highest contentof xylene, which is 10.4% higher than the physical mixture. And the ZSM-5/β co-crystalline zeolitehas better selectivity for toluene alkylation and weaker de-methylation than β zeolite, ZSM-5 andtheir physical mixture.

Effect of Alkali Treatment on the Structure and Catalytic Properties of ZSM-5 Zeolite

Catalytic properties of ZSM-5 zeolite samples pretreated with NaOH solution have been investigated. The samples are characterized by XRD, SEM, chemical analysis, and N2 adsorption. The results indicate that mesopores are created in ZSM-5 crystals under alkali treatment without change the microporous structure and acidic strength of the zeolite, but the crystallinity is greatly decreased under severe treatment. IR indicates that the concentration of silanol is greatly enriched by alkali treatment. The etherification activities of ZSM-5 zeolites are greatly increased by alkali-treatment. The noticeably improved catalytic activity of treated samples is ascribed to the formation of mesopores and greatly enriched silanol group.