Thermal-catalytic degradation kinetics of polypropylene over BEA,ZSM-5 and MOR zeolites

In this study, thermal degradation of additive-free polypropylene powder over different type of zeolite catalysts was investigated. BEA, ZSM-5 and MOR with different surface areas, pore structures, acidities and Si/Al molar ratios were used as solid catalysts for degradation of polypropylene (PP). Degradation rate of the PP over zeolites was studied by thermogravimetric analysis (TGA) employing four different heating rates and apparent activation energies of the processes were determined by the Kissinger equation. The catalytic activity of zeolites decreases as BEA > ZSM-5a (Si/Al = 12.5) > ZSM-5b (Si/Al = 25) > MOR depending on pore size and acidity of the catalysts. On the other hand, initial degradation is relatively faster over MOR and BEA than that over both ZSM-5 catalysts depending on the apparent activation energy. It can be concluded that acidity of the catalyst is the most important parameter in determining the activity for polymer degradation process as well as other structural parameters, such as pore structure and size.     

Catalytic degradation of polypropylene I. Screening of catalysts

The catalytic degradation of polypropylene has been investigated in this study. Solid acid catalysts, such as silica-alumina and zeolites (HZSM-5, natural zeolite, Mordenite etc.), were screened for polypropylene degradation in the range of 350-450‡C. The degradation products of polypropylene, especially a liquid fraction, formed over solid acid catalysts, were analyzed by GC/MS. The degradation products are distributed in a narrow range of carbon number compared with those obtained by thermal degradation. The liquid fraction contained large amounts of iso-paraffins and aromatics as are present in the gasoline traction of petroleum. The natural zeolite catalyst (clinoptilolite structure, occurring in Youngil area of Korea) was an efficient catalyst for the polypropylene degradation. The acidity and characteristic pore structure of this zeolite appear to be responsible for the good performance. The effects of temperature and reaction tune on the product distribution have also been studied in this work.     

Catalytic cracking of n-octane over zeolites with different pore structures and acidities

Catalytic cracking of n-octane has been studied over FAU, FER, MWW, MFI, BEA and MOR zeolites in order to investigate the effects of pore structure and acidity on their catalytic properties. The conversion of n-octane was largely dependent on the number of strong acid sites, while their pore structure determined the rate of catalyst deactivation due to carbon deposit. Continuous and high catalytic activity, therefore, was obtained on the MFI zeolite with sinusoidal pores and small Si/Al molar ratio, because its pores suppress the formation of large intermediate and its large number of strong acid sites accelerates the cracking of n-octane     

Acidity and catalytic activity of mesoporous ZSM-5 in comparison with zeolite ZSM-5, Al-MCM-41 and silica–alumina

Acidity of mesoporous HZSM-5 prepared using amphiphilic organosilane template molecules was measured. Brønsted acid sites were observed in the prepared sample, and the number and the strength of Brønsted acid sites were determined quantitatively by a method of infrared-mass spectroscopy/temperature-programmed desorption (IRMS-TPD) of ammonia. ΔH for ammonia adsorption as an index of the strength was ca. 150 kJ mol⁻¹ that was almost the same as on usual HZSM-5, but the number was smaller than that of HZSM-5. From the measured acidity, it was concluded that the mesoporous materials contained a smaller concentration of Brønsted acid site notable on the structure of HZSM-5. Measurements of turnover frequency (TOF) in the catalytic cracking of octane supported the conclusion. Density functional calculations showed that the defect sites Al–OH and Si–OH attached to the Brønsted acid site changed the strength of the acid sites to show some possible structures of the weak and strong Brønsted acid sites included in the mesoporous HZSM-5. Acidities of Al-MCM-41 and silica–alumina were also measured, and the difference in the solid acidities of these materials was discussed.     

Photo-oxidative degradation of polypropylene/montmorillonite nanocomposites

The photo-oxidative behavior of the polypropylene (PP)/montmorillonite (MMT) nanocomposites and microcomposites has been investigated upon ultraviolet exposure using the technique of infrared spectroscopy. The rate of photo-oxidative degradation of PP/MMT nanocomposites is much faster than that of pure PP. The influence of pristine MMT, alkylammonium and compatibilizer were investigated, respectively. All these components can catalyze the photo-oxidation of PP matrix, in which the influence of compatibilizer and pristine MMT is primary. Moreover, the dispersion state of the clay particles in the polymer matrices has a little influence on the photo-oxidative degradation of polymer matrix. Consequently, an integrated catalysis mechanism of the photo-oxidative degradation of PP clay nanocomposite is proposed. It would provide benefit direction for the preparation and usage of polymer layered silicate nanocomposites (PLSN).     

Selective toluene disproportionation over ZSM-5 zeolites

Selective toluene disproportionation to benzene and xylenes is investigated over HZSM-5 and modified HZSM-5 zeolites. The zeolites are modified with nickel, magnesium, phosphorus and boron, characterised by sorption, acidity measurement and X-ray photoelectron spectroscopy, and their activity towards toluene disproportionation is discussed in the light of their physico-chemical properties. The two types of active sites have been identified; one promoting disproportionation and the other cracking and dealkylation of toluene. It is found that the latter sites are suppressed due to incorporation of the modifiers. The modified zeolites are found to be para-selective which appears to be consistent with the commonly accepted view that modifiers like magnesium, phosphorus and boron reside in the channels and react with Brønsted acid sites, leading to partial blockages and thus favouring the formation of p-xylene. The effect of poisoning the zeolite with 1-methylisoquinoline is also investigated. In the case of poisoned catalyst, p-xylene is produced at levels up to 99%. The total elimination of other isomers from the products is suggested due to the selective poisoning of the non-selective sites (on the external crystal surface) and to partial blocking of the pore openings.     

Infrared spectroscopic study of the acid properties of dealuminated BEA zeolites

A series of HBEA samples were prepared by dealumination through three different methods (steaming, treatments with hydrochloric acid and ammonium hexafluorosilicate (HFS) solutions) of a parent sample with total and framework Si:Al ratios of 12.5 and 33, respectively, constituted of 20 nm crystallites. The samples were characterized by XRD, nitrogen adsorption and pyridine adsorption–desorption followed by IR spectroscopy. Whereas the three dealumination treatments have practically no effect on crystallinity and nitrogen adsorption properties, they cause large changes in the ranges of the O–H bond stretching modes (3300–3800 cm⁻¹) and of the most intense IR absorption of pyridine (1400–1700 cm⁻¹). Treatments with HCl or HFS cause the most significant changes: disappearance of the 3662 and 3782 cm⁻¹ bands corresponding to extraframework Al species and to tricoordinated Al species partially connected to the framework, respectively, appearance of additional bands at 1603 and 1446 cm⁻¹ ascribed to a new type of pyridine species coordinated to Lewis sites (PyL₂) and for desorption temperatures above 350 °C, of a band at 1462 cm⁻¹ generally ascribed to iminium ions, apparently at the expense of the PyL₂ band. In agreement with this formation of iminium ions, desorption at high temperatures causes the complete disappearance of pyridinium ions without complete restoration of the acidic bridging hydroxyl band. PyL₂ species are proposed to be pyridine molecules coordinated to Lewis sites and interacting through hydrogen bond with protonic sites.     

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.     

Mechanistic study of organic template removal from ZSM-5 precursors

The decomposition mechanism of tetrapropylammonium (TPA⁺) template cations in several commercial ZSM-5 precursors was studied by temperature-programmed desorption/oxidation using a mass spectrometer (TPD/TPO-MS). Different oxygen concentrations, gas flow rates and temperature ramp rates were examined to understand the effects of these factors on the organic template decomposition. The TPA⁺ template decomposition pattern is strongly dependent on the SiO₂/Al₂O₃ molar ratio (SAR) and the oxygen concentration. The TPA⁺ template cations may be associated with three different sites depending on the SAR: Lewis acid sites (surface Al–O⁻), Brønsted acid sites (framework Al–O⁻), and weakly acidic Si---O⁻ sites. The thermal decomposition of TPA⁺ templates at different sites produced different products, including water, ammonia, propylene, ethylene, methane, and n- and iso-propylamines. However, no significant heavy volatile compounds were detected, suggesting that secondary reactions (e.g., oligomerization of olefins) were extremely limited and negligible in a fixed-bed micro-reactor used for TPD/TPO. The TPD-MS results suggest that the thermal decomposition mechanism on Lewis acid sites is possibly a free radical type of reaction, while on Brønsted acid sites and Si---O⁻ sites, the decomposition undergoes both Hoffman elimination reaction and a radical type of reaction. The presence of oxygen significantly lowered the TPA⁺ decomposition temperature, which is also a function of oxygen concentration. The knowledge about the template decomposition pattern and the composition of the evolved volatiles obtained by the TPD/TPO-MS technique may be used to develop ideal organic template removal procedures for zeolites.     

ZSM-5沸石分子筛脱硫脱氮机理及改性方法

综述了近年分子筛的脱硫脱氮机理及动力学,从表面酸性和孔结构两方面评述了ZSM-5分子筛的改性。重点综述了基于ZSM-5的杂原子分子筛、分子筛膜、纳米分子筛的研究动态和发展趋势,指出了研究应用中存在的问题以及今后的研究方向。     

Comparative study of pure component adsorption of linear alkanes in zeolites MFI, BEA and MOR

Grand canonical Monte Carlo (GCMC) simulations and configurational-bias Monte Carlo simulations (CBMC) have been performed to compute and compare the pure component adsorption isotherms of C1–C7 linear alkanes in MFI, BEA, and MOR zeolites at 300 K. It is demonstrated that generally, the surfaces of the three zeolites available for adsorption are not energetically homogeneous; adsorption of the alkanes in the three zeolites can be divided into two steps, in the first step of which molecules are adsorbed in the strong sites and on the later of which on the weak sites; all isotherms obtained can be well described by the dual-site Langmuir equation, though the saturation loadings and the adsorption strengths are different for the three different topologic zeolites. A quantitative analysis of the isotherms shows that the Henry’s law constants in the three zeolites obey a similar linear relation to the number of carbon atoms of the alkanes.     

Hydrodesulfurization over noble metals supported on ZSM-5 zeolites

Pt/HZSM-5 showed high and stable catalytic activity for the hydrodesulfurization of thiophene at 400°C and its catalytic activity was higher than that of commercial CoMo/Al₂O₃ catalyst. Pt/HZSM-5 zeolite was not poisoned by hydrogen sulfide in the hydrodesulfurization of thiophene and hydrocracking of hydrocarbons. The catalytic activity of Pt/HZSM-5 decreased with increase of SiO₂/Al₂O₃ ratio in HZSM-5. The Brønsted acid site of HZSM-5 and spillover hydrogen formed on Pt particle in Pt/HZSM-5 catalyst play an important role for the hydrodesulfurization of thiophene.     

Obtaining hydrocarbons from ethanol over iron-modified ZSM-5 zeolites

The search for new energy sources has impulsed hydrocarbon production from methanol and ethanol over ZSM-5 zeolites. Iron incorporation by different methods has led to a variety of chemical applications. Thus, hydrocarbon production from ethanol was studied over a ZSM-5 zeolite modified by ion exchange and impregnation with iron. XRD, FTIR, TPR, nitrogen adsorption, Mössbauer and photoacoustic spectroscopies were used for the samples characterization. The highest yield of liquid hydrocarbons was obtained with the low iron-exchanged zeolite, especially co-feeding hydrogen. The calcination procedure led to a migration of the iron species, probably forming iron oxide particles.     

Gas adsorption properties of ZSM-5 zeolites heated to extreme temperatures

Zeolites are broadly useful catalysts and molecular sieve adsorbents for purification. In this work the thermal degradations of bare and platinum-loaded ZSM-5 was studied with the goal of understanding the behavior of nanoporous solids at extreme temperatures comparable to those present in nuclear fuels. Zeolites were heated in air and nitrogen at temperatures up to 1500 °C, and then characterized for thermal stability via X-ray diffraction (XRD) and for gas adsorption by the Brunauer-Emmett-Teller (BET) method. Scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA) were also employed. These results indicate zeolites are stable when heat-treated up to 800 °C and degrade slowly at higher temperatures. However, significant surface area degradation begins at 1025–1150 °C with an activation energy of 400 kJ/mole. At 1500 °C, gas adsorption measurements and SEM images show complete collapse of the porous structure. Critically for nuclear fuel applications, however, the zeolites still adsorb helium in significant quantities.     

超微ZSM-5分子筛的合成

将原料硫酸铝、硅酸钠以及模板剂按不同配比,在实验室采用常规加热温度和压力合成超微ZSM-5分子筛,采用静态苯吸附、XRD、SEM和IR等表征方法对所得样品进行表征,结果表明,合成的产品从晶体结构符合ZSM-5分子筛的典型结构,颗粒大小达到超微分子范围。     

Pyrolysis and co-pyrolysis of Laminaria japonica and polypropylene over mesoporous Al-SBA-15 catalyst

The catalytic co-pyrolysis of a seaweed biomass, Laminaria japonica, and a typical polymer material, polypropylene, was studied for the first time. A mesoporous material Al-SBA-15 was used as a catalyst. Pyrolysis experiments were conducted using a fixed-bed reactor and pyrolysis gas chromatography/mass spectrometry (Py-GC/MS). BET surface area, N₂ adsorption-desorption isotherms, and NH₃ temperature programmed desorption were measured to examine the catalyst characteristics. When only L. japonica was pyrolyzed, catalytic reforming slightly increased the gas yield and decreased the oil yield. The H₂O content in bio-oil was increased by catalytic reforming from 42.03 to 50.32 wt% due to the dehydration reaction occurring on the acid sites inside the large pores of Al-SBA-15. Acids, oxygenates, mono-aromatics, poly aromatic hydrocarbons, and phenolics were the main components of the bio-oil obtained from the pyrolysis of L. japonica. Upon catalytic reforming over Al-SBA-15, the main oxygenate species 1,4-anhydro-d-galactitol and 1,5-anhydro-d-manitol were completely removed. When L. japonica was co-pyrolyzed with polypropylene, the H₂O content in bio-oil was decreased dramatically (8.93 wt% in the case of catalytic co-pyrolysis), contributing to the improvement of the oil quality. A huge increase in the content of gasoline-range and diesel-range hydrocarbons in bio-oil was the most remarkable change that resulted from the co-pyrolysis with polypropylene, suggesting its potential as a transport fuel. The content of mono-aromatics with high economic value was also increased significantly by catalytic co-pyrolysis.     

Conversion of light paraffins for preparing small olefins over ZSM-5 zeolites

The conversion of C₃-C₉ paraffins to small olefins over ZSM-5 zeolite is investigated. The small olefins are primary products and are usually converted into other more stable secondary products such as aromatics on the ZSM-5 zeolites. Thermally treated HZSM-5, K/HZSM-5 and Ba/HZSM-5 catalysts were developed and favourable oxidative conditions were introduced for the conversion process to maximize selective conversion of light paraffins to small olefins at the relatively low temperature of 873 K. The role of K and Ba is to minimize bimolecular hydrogen transfer reactions and enhance the dehydrogenation activity of the catalysts. Meanwhile, the oxygen in the gas phase is effective to improve the olefin selectivity and yield. C₂-C₄ olefin selectivities of 70.4 and 66.8% have been obtained for propane andn-hexane feed-stocks, respectively, at a temperature of 873 K.     

Dealumination kinetics of composite ZSM-5/mordenite zeolite during steam treatment: An in-situ DRIFTS study

To get a better understanding of structural deactivation of ZSM-5/MOR during the catalytic cracking of n-heptane in the steam atmosphere, a comprehensive mechanism of hydrothermal dealumination was proposed through in-situ diffuse reflectance Fourier transform infrared spectroscopy(DRIFTS) in this work. The mechanism can be divided into two steps: firstly, the hydrolysis of four Al\\O bonds, and secondly, the self-healing of Si\\OH bonds accompanied with partial condensation of the extra-framework Al species. Accordingly, the kinetics of dealumination process has also been fully discussed. In the IR spectra, the range of 3450–3850 cm~(-1) could be deconvolved to distinguish the hydroxyl groups on the different position and calculate the consumption of each hydroxyl group during the reaction. Based on results from the in-situ DRIFTS, the kinetics of dealumination was hence developed and also in well agreement with the kinetics of deactivation of ZSM/MOR catalysts during the reaction in the presence of little coke deposits.     

介-微孔ZSM-5分子筛的原位合成

在ZSM-5合成过程中引入高分子量三嵌段共聚物P123,原位合成介-微孔ZSM-5分子筛,采用XRD、IR、BET和TEM对材料进行表征。结果表明,合成材料的主体结构为ZSM-5分子筛,比表面积为372 m²·g^-1,孔体积为0.226 mL·g^-1,其中,介孔比表面积为44 m²·g^-1,介孔孔体积为0.068 mL·g^-1,为介-微孔分子筛的合成开发了一条全新的技术路线。