Vapor‐Phase Transport Crystallization of Micro‐HZSM‐5 Zeolite Coatings

A novel structured catalyst of binderless micro‐HZSM‐5 zeolite coating was prepared on stainless‐steeled tubes (i.d. 2 mm) through wash coating and vapor‐phase transport (VPT) crystallization method. The subsequent crystallization of amorphous SiO₂ binders improved the coatings adhesion tremendously by more than 10 times with the least amount of binders (<20% by weight), attributed to the remarkably enhanced interlock by the formed Mordenite Framework Inverted structure between zeolite particles. Catalytic cracking of supercritical n‐dodecane (500°C, 4 MPa) was used to examine the catalytic performance of the coatings as prepared, indicating that MZC‐V0.2 exhibited a catalytic activity improvement by 8% and a decreased deactivation rate by 48%. The improved catalytic performance may result from its high acid sites amount by incorporating extra‐framework Al into HZSM‐5 framework, and the possible depressing of pore‐mouth deactivation through partial modification of surface acid sites during VPT treatment. This work provides a potential technique to prepare mechanically stable zeolite coatings with high catalytic activity but less binder usage.     

Controllable fabrication and catalytic activity of highly b‐oriented HZSM‐5 coatings

Multilayer b‐orientated HZSM‐5 catalytic coating is controllably synthesized by repeated growth of zeolite layer on Ti?OH‐modified surface of sublayer. The as‐prepared zeolite coating shows performance enhancement up to 110% in catalytic cracking of n‐dodecane ascribed to enhanced mass transfer in its straight and short pathway along the b‐axis. © 2014 American Institute of Chemical Engineers AIChE J, 60: 1964–1968, 2014     

Washcoating of Different Zeolites on Cordierite Monoliths

Cordierite monoliths were washcoated with slurries of different zeolites (ZSM5, β zeolite, mordenite, and Zeolite Y) in order to establish the relationship between washcoat characteristics and the powder and slurry properties. To achieve this objective, initially, the zeolite particle size was reduced to 2–3 μm by wet ball milling, and during this process the crystallinity and surface area of the powder were not significantly affected. The rheological behavior of the zeolite slurries is a function of the type of zeolite and solid content. The washcoat properties, such as loading, thickness, uniformity, and reproducibility, depend on the particle size of the powder, number of immersions, slurry concentration, slurry viscosity, and surface tension. The mechanical stability of the zeolite washcoat decreases with an increase in cumulative loading and slurry particle size. Addition of binder (colloidal silica) results in an improvement in zeolite loading and washcoat adherence.     

Controllable fabrication and catalytic performance of nanosheet HZSM‐5 films by vertical secondary growth

Nanosheet HZSM‐5 film vertically grown on the substrate with the tailorable macro‐ and meso‐pores between the layers of nanosheets is hydrothermally synthesized by seed‐assisted secondary growth method. The as‐prepared nanosheet HZSM‐5 film exhibits reaction rate enhancement up to 312% in catalytic cracking of n‐dodecane as well as twice light olefins selectivity, ascribed to the better mass transfer of reactants in the hierarchical porous structure and the ultra‐thin b‐axis pores of nanosheets. © 2018 American Institute of Chemical Engineers AIChE J, 64: 1923–1927, 2018     

Dispersion and stability of SiC ceramic slurry for stereolithography

Stereolithography based additive manufacturing provides an effective method to fabricate complex-shaped SiC ceramic components. The dispersion and stability of the ceramic slurry are very important for stereolithography. In this study, the dispersion and stability of SiC ceramic slurries were investigated systematically. The effects of resin monomers, dispersants, particle size, solid loading and ball milling time on the dispersion, rheological behavior and stability of SiC ceramic slurries were studied in detail. Finally, an optimal SiC ceramic slurry for stereolithography based additive manufacturing was obtained, and complex-shaped SiC ceramic architectures were fabricated.     

Chemical kinetic modeling of i‐butane and n‐butane catalytic cracking reactions over HZSM‐5 zeolite

A chemical kinetic model for i‐butane and n‐butane catalytic cracking over synthesized HZSM‐5 zeolite, with SiO₂/Al₂O₃ = 484, and in a plug flow reactor under various operating conditions, has been developed. To estimate the kinetic parameters of catalytic cracking reactions of i‐butane and n‐butane, a lump kinetic model consisting of six reaction steps and five lumped components is proposed. This kinetic model is based on mechanistic aspects of catalytic cracking of paraffins into olefins. Furthermore, our model takes into account the effects of both protolytic and bimolecular mechanisms. The Levenberg–Marquardt algorithm was used to estimate kinetic parameters. Results from statistical F‐tests indicate that the kinetic models and the proposed model predictions are in satisfactory agreement with the experimental data obtained for both paraffin reactants. © 2011 American Institute of Chemical Engineers AIChE J, 58: 2456–2465, 2012     

Correlation between yttria stabilized zirconia particle size and morphological properties of NiO–YSZ films prepared by spray coating process

A systematic approach was taken to investigate the morphology of NiO–yttria stabilized zirconia (YSZ) films deposited by a spray coating process. The final morphological aspects of anode films were influenced by the particle size of YSZ powders and the milling time of the slurries used for film deposition. YSZ powders with average particle size of 17 and 52 nm were obtained from powders calcined at 800 and 1000 °C, respectively. The results obtained by rheological studies pointed out that slurries prepared from YSZ powders calcinated at 1000 °C and milling time of 20 h had more stability. All slurries presented thixotropic and pseudoplastic behaviors.     

Optimized experimental design for natural clinoptilolite zeolite ball milling to produce nano powders

Nano powder of natural clinoptilolite zeolite was mechanically prepared by using a planetary ball mill. Statistical experimental design was applied to optimize wet and dry milling of clinoptilolite zeolite. To determine appropriate milling conditions with respect to the final product crystallinity, particle size and distribution, different milling parameters such as dry and wet milling durations, rotational speed, balls to powder ratio and water to powder ratio (for the wet milling) were investigated. Laser beam scattering technique, scanning electron microscopy and X-ray diffraction analyses were carried out to characterize samples. Results showed that larger than 1 mm particle size of clinoptilolite powder may mechanically be reduced into the size range of less than 100 nm to 30 μm by means of planetary ball milling.     

不同配制方法下剪切增稠液体的性能表征

本文用原生粒径20 nm、团聚现象严重的纳米SiO2作为分散相,PEG200作为分散介质,分别用超声波法和行星式球磨法来配制用于个体防护装甲的剪切增稠液体.通过激光粒度分析仪和哈克流变仪测定不同配制方法下纳米SiO2/PEG200分散体系的分散性和流变性能,结果表明:由于行星式球磨的连续细化作用和分散剂A1120的助磨、保护颗粒新表面的作用,用行星式球磨法加入分散剂A1120配制的剪切增稠液体,纳米SiO2在体系中的平均粒径最小,分散性好;分别用行星式球磨法和超声波法加入分散剂A1120配制的剪切增稠液体均具有先剪切变稀后剪切增稠的流变性能,但在整个剪切应力范围内,行星式球磨法配制的剪切增稠液体的粘度比超声波法大.     

Converting Alkali Lignin to Biofuels over NiO/HZSM‐5 Catalysts Using a Two‐Stage Reactor

A series of NiO/HZSM‐5 catalysts were used to convert alkali lignin to hydrocarbon biofuels in a two‐stage catalytic pyrolysis system. The results indicated that all NiO/HZSM‐5 catalysts reduced the content of undesirable phenols, furans, and alcohols of the biofuel compared to non‐catalytic treatment. The NiO/HZSM‐5 catalyst with the lowest amount of NiO generated the highest biofuel yield in all catalytic treatments, and it also produced biofuel with the highest content of hydrocarbons. The emission of carbon oxides (CO and CO₂) increased in the treatments with higher‐NiO loading HZSM‐5 due to the redox reaction between NiO and the oxygenated compounds in the bio‐oil. Ni₂SiO₄ was generated in the used NiO/HZSM‐5 catalysts during the high‐temperature pyrolysis process.     

催化裂化汽油裂解制丙烯

以催化裂化汽油为原料,水热处理后的HZSM-5分子筛为催化剂,催化裂解制丙烯。比较了水热处理后的HZSM-5分子筛催化剂上负载镧和未负载镧的催化裂化性能,并考察了镧的最佳负载量。结果表明,水热处理后负载镧提高了催化剂活性、稳定性和丙烯选择性,负载镧质量分数为8%时,催化裂化性能最佳。当反应温度550 ℃和空速4 h-1时,丙烯收率12.51%。     

Catalytic Activity of Copper Oxide Impregnated HZSM‐5 in Methanol Conversion to Liquid Hydrocarbons

A number of CuO/HZSM‐5 catalysts have been studied in a small scale fixed bed reactor for the conversion of methanol to gasoline range hydrocarbons at 673 K and at one atmospheric pressure. All the catalysts were prepared by wet impregnation technique. The copper oxide loading over HZSM‐5 (Si/Al=45) catalyst was studied in the range of 0 to 9 wt%. XRD, surface area analyzer, metal trace analyzer, SEM techniques and TGA were used to characterize the catalysts. Incorporation of CuO onto HZSM‐5 zeolite significantly increased conversion and liquid hydrocarbon product yields. The major liquid products of the reactions were ethyl benzene, toluene, xylene, isopropyl benzene, ethyl toluene, trimethyl benzene and tetramethyl benzene. The maximum methanol conversion and hydrocarbon product yield was obtained at a copper oxide loading of 7 wt%. Effect of run time on conversion and product distribution was also investigated to compare the performance of these catalysts and coke on the catalyst was determined. Effect of space‐time and temperature on methanol conversion and products yield with 7 wt% CuO/HZSM‐5 has also been investigated and analyzed qualitatively.     

Influence of particle size distribution on rheology and particle packing of silica-based suspensions

The effect of particle size, particle size distribution and milling time on the rheological behaviour and particle packing of silica suspensions was investigated using slurries containing total solids loading of 46 vol.%. Three silica powders with different average particle sizes (2.2, 6.5 and 19 μm), derived from dry milling of sand, and a colloidal fumed silica powder with 0.07 μm were used. Different proportions of colloidal fumed silica powder were added to each of the coarser silica powders and the mixtures were ball-milled for different time periods. The influence of these factors and of the particle size ratio on the rheological behaviour of the suspensions and densities of green slip cast bodies was studied.The results show that the flow properties of slips are strongly influenced by the particle size distribution. The viscosity of suspensions increases with the addition of fine particles, imposing some practical limitations in terms of volume fraction of fines that can be added. On the other hand, increasing the size ratio enhanced the shear thinning character of the suspensions, while decreasing the size ratio led to an accentuation of the shear thickening behaviour. For all mixed suspensions, green densities increased with increasing milling time, due to size reduction of silica powders and a more efficient deagglomeration of fumed silica. Increasing amounts of fumed silica led to a first increase of particle packing up to a maximum, followed by a decreasing trend for further additions. Good relationships could be observed between rheological results and packing densities.     

Zeolite Beta with hierarchical porosity prepared from organofunctionalized seeds

Beta zeolite with hierarchical porosity has been obtained by a new synthesis strategy, based on perturbing the growth of the zeolite crystals by functionalization of the zeolitic seeds with organosilanes in order to hinder and prevent their further aggregation and agglomeration. As a consequence, a secondary porosity in the supermicropore region has been generated in zeolite Beta, leading to a considerable increase in both the total surface area and the pore volume of the material. The enhancement of the textural properties can be controlled by changing the silanization agent molecular size and its quantity added to the synthesis medium. This type of hierarchical Beta zeolites presents interesting applications as catalysts in reactions involving bulky molecules. Thus, their catalytic activity in the catalytic cracking of LDPE has been found to be strongly enhanced compared to a standard Beta zeolite sample, due to the higher accessibility to the acid sites caused by the presence of the secondary porosity.     

High‐temperature mechanical behavior of ZrB2‐based composites with micrometer‐ and nano‐sized SiC particles

Using micrometer‐ and nano‐sized SiC particles as reinforcement phase, two ZrB₂‐SiC composites with high strength up to 1600°C were prepared using high‐energy ball milling, followed by hot pressing. The composite microstructure comprised finer equiaxed ZrB₂ and SiC grains and intergranular amorphous phase. The temperature dependency of flexure strength related to the initial particle size of SiC. In the case of micrometer‐sized SiC, the high‐temperature strength was improved up to 1500°C compared to room‐temperature strength, but the strength degraded at 1600°C, with strength values of 600‐770 MPa. In the case of nano‐sized SiC, the enhanced high‐temperature strength was observed up to 1600°C, with strength values of 680‐840 MPa.     

Effects of Particle Size on Electromagnetic and Microwave Absorption Properties of La0.7Sr0.3MnO3±δ‐Epoxy Composite

La_0.7Sr_0.3MnO_3±δ powders were fabricated by solid‐state reaction method at 1473 K for 4 h. The precursors were prepared by ball‐milling raw materials for 3, 6, 9, and 12 h, respectively. The crystal structures, particle size, and morphologies of precursors and prepared La_0.7Sr_0.3MnO_3±δ were characterized by XRD, laser particle size analyzer and SEM, respectively. It is found that La_0.7Sr_0.3MnO_3±δ possessed large particle size by ball‐milling raw materials for a long time. Results indicated that La_0.7Sr_0.3MnO_3±δ, synthesized by ball‐milling raw materials for 3 h, exhibited the optimal microwave absorption properties. The maximum reflection loss was ?28.8 dB, and the ?6 dB absorption bandwidth was 5.80 GHz.     

Bio‐Oil as a Potential Biomass‐Derived Renewable Raw Material for Bio‐Phenol Production

A route for directional conversion of bio‐oil into phenol by means of coupling the catalytic cracking of the bio‐oil with the hydroxylation of the bio‐oil‐based benzene‐rich aromatics is proposed. High selectivity for phenol in the resulting organic liquid was achieved, with an almost complete conversion of the bio‐oil. Co‐cracking of the bio‐oil with methanol over a Zn‐modified zeolite significantly enhanced the yields of aromatics and decreased the deactivation of the catalyst during the catalytic cracking of the bio‐oil. The phenol yield depended on the metal oxide catalysts, the temperature, and the reaction time during hydroxylation of the benzene‐rich aromatics. The reaction pathway of converting bio‐oil into phenol was elucidated based on the products identified and the characterization of the catalysts.     

Wet jet milling of Al2O3 slurries

A wet jet milling process was employed as a novel method to prepare ceramic slurries. The wet jet milling pulverized raw materials to primary particle size within a short time. The wet jet-milled slurries showed very low viscosity, as comparing to ball-milled slurries. Moreover, the viscosity of wet jet-milled slurries was stable for long times, whereas that of ball-milled slurries increased rapidly with increase in the time. Al₂O₃ particles after wet jet milling kept initial surface conditions, though Al₂O₃ particles after ball milling yielded more OH groups on the surface. The relative density of the green bodies prepared from the wet jet-milled slurries was about 65% or more without depending on the solid content of slurry. On the other hand, the relative density of the green bodies fabricated by the ball-milled slurries increased with the slurry solid content, and it reached more than 60% at 50 vol% of solid content.     

Milling‐induced esterification between cellulose and maleated polypropylene

The ball milling of cellulose and maleic anhydride grafted polypropylene (MAPP) induced the formation of ester bonds between OH groups of cellulose and maleic anhydride groups of MAPP, in marked contrast to the melt mixing of the original cellulose and MAPP, through which the esterification was hardly observed. This esterification was hardly dependent on the chemical structure of MAPP. In agreement with the enhanced interfacial adhesion due to the formation of ester bonds, a composite prepared via ball milling revealed an improvement in the tensile strength with respect to a melt‐mixed composite. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1703–1709, 2004     

Recycling and application of wasted polytetrafluoroethylene via high‐energy ball milling technology for nitrile rubber composites preparation

Wasted polytetrafluoroethylene fibers were recycled using high‐energy ball milling technique, and the recylced polytetrafluoroethylene (r‐PTFE) was employed to prepare nitrile rubber (NBR)/r‐PTFE composites. The structure of r‐PTFE and properties of NBR/r‐PTFE composites were investigated by polarized optical microscope, laser particle size analyzer, differential scanning calorimetry, and scanning electron microscopy, respectively. The results show that increasing the milling time from 4 to 7 h leads to decreasing the average particle size, the degree of crystallinity and the number‐average molecular weight of r‐PTFE, whereas no obvious change is found by further prolonging the milling time. It is also clear that the NBR/r‐PTFE composite with the r‐PTFE obtained from a longer milling time possesses a higher mechanical and solvent resistance property. Compared with pure NBR, NBR/r‐PTFE composites with r‐PTFE for 7 h milling show a 21.9% increase in modulus at 300% and 27.8% decrease in swelling index. POLYM. ENG. SCI., 56:643–649, 2016. © 2016 Society of Plastics Engineers