Influence of binder on catalytic performance of Ni/HZSM-5 for hydrodeoxygenation of cyclohexanone

The influences of binders (alumina, silica sol, kaolin) on the performance of Ni/H-ZSM-5 for hydrodeoxygenation of cyclohexanone were investigated in a fixed-bed reactor. N₂ sorption, X-ray diffractions, H₂-temperature-programmed reduction, transmission electron microscopy, ²⁷Al MAS NMR, and temperature-programmed desorption of ammonia were used to characterize the catalysts. The obtained results exhibited that porosity and acidity of the catalysts were strongly influenced by the binders. The most outstanding catalytic performance was observed on catalyst with alumina binder, which bears a well-developed pore structure and more acid sites than the others. Thus, alumina was chosen as the optimum binder to Ni/HZSM-5.     

Fe_2O_3/HZSM-5催化转化乙醇制备低碳烯烃

采用浸渍法制备了Fe2O3/HZSM-5分子筛催化剂,并用于乙醇脱水与低聚制备丙烯为主的低碳烯烃反应体系.在400～500℃范围内考察了HZSM-5的硅/铝比、氧化铁负载量、反应温度、催化剂氢气还原预处理对产物中烯烃收率的影响.结果表明,HZSM-5硅/铝比为140时,丙烯、丁烯收率最高;氧化铁负载能有效提高烯烃收率,当负载量为2.9%时丙烯收率最高,接近25%;反应初期升高温度可促进丙烯生成,但催化剂寿命缩短;氢气还原预处理能进一步促进乙烯、丙烯生成.     

Enhanced Stability and Propene Yield in Propane Dehydrogenation on PtIn/Mg(Al)O Catalysts with Various In Loadings

The dehydrogenation of propane on In-promoted Pt (0.3 wt% Pt) supported on hydrotalcite Mg(Al)O with different In loadings (0.2–1.0 wt% In) was investigated at 550 °C atmospheric pressure. All the bimetallic PtIn/Mg(Al)O showed higher propane conversion and propene selectivity than the Pt/Mg(Al)O with Pt0.8In exhibited the best catalytic performances with 97.5% propylene selectivity and 27.5% yield after 5 h time-on-stream. The addition of In to the monometallic Pt catalyst could reduce the acidity strength especially the strong acid site. As revealed by the H₂-TPR and XPS results, addition of In by impregnation on Pt/Mg(Al)O also led to the formation of metallic In and PtIn alloy, which greatly enhanced the catalyst activity and reduced coke formation on the support. Nevertheless, excessive In loading (i.e., Pt1.0In) resulted in a descending trend of catalyst activity compared to the Pt0.8In, due probably to the large amount of metallic In being formed, which was disadvantageous in propane dehydrogenation.     

Effect of nickel incorporation on the acidity and stability of HZSM-5 zeolite in the MTO process

A study has been carried on the effect of Ni incorporation on the acidity (acid strength distribution and total acidity), on the hydrothermal stability of a HZSM-5 zeolite and on the kinetic performance of this catalyst in the MTO process at high temperature (up to 500 °C, in order to increase selectivity to olefins) and when there is a high water content in the feed (in order to minimise deactivation by coke). The incorporation of Ni in the HZSM-5 zeolite implies a decrease in the total acidity and in the acid strength of the zeolite and, consequently, the activity of the catalyst decreases. Nevertheless, the catalysts with Ni are hydrothermally more stable than the parent zeolite catalyst. A Ni content around 1 wt% is the optimum, as it allows for uninterrupted operation in reaction–regeneration cycles, with water contents higher than 50 wt% in the medium, without irreversible deactivation, whereas a higher Ni content produces an unnecessary loss of initial activity.     

Higher Alcohol Synthesis Using K-Doped CoRhMoS2/MWCNT Catalysts: Influence of Pelletization,Particle Size and Incorporation of Binders

In this study, alkalinized MWCNT supported MoS₂ catalysts have been doubly-promoted with Co and Rh. Catalysts were prepared by the conventional co-impregnation method and stabilized under argon atmosphere. Characterization of the oxidic samples by BET revealed that the mesoporosity of the pristine MWCNT support was not compromised after loading a combined total of 30 wt% metals (9 wt% K, 4.5 wt% Co, 1.5 wt% Rh, and 15 wt% Mo) on the support; however, a significant decrease in specific surface area was observed. Broad angle XRD analysis confirmed the homogenous dispersion of catalyst metals on the support. Two catalyst grain sizes were first investigated to elucidate the effect of particle size: a finely ground powder (88 μm) and a pelletized form (1,780 μm). Despite the total alcohol yield of 0.261 g/(g_cat h) observed by conducting higher alcohol synthesis reaction at T = 330 °C, P = 8.3 MPa, H₂/CO = 1.25, and GHSV = 3.6 m _STP ³ /(kg_cat h) for the fine powdered sample, the relatively higher pressure drop could be minimized by using the pelletized form of the catalyst. Finally, a systematic study of variety of selected binders was conducted to gain insight of catalyst’s applicability for industrial purposes. Three selected binders namely: bentonite clay, coal tar, and humic acid were thus investigated; taking into consideration significant factors such as melting point and binder requirement per catalyst support. The CO conversions evaluated for the two binder-free catalysts (88 and 1,700 μm) showed that the catalyst with fine particle sizes (88 μm) performed better than that in the pelletized form (binder-free, 1,700 μm); yielding a maximum ethanol selectivity of 38.5 % at steady-state reaction conditions.     

The role of shape selectivity and intrinsic selectivity of acidic sites of the catalysts in the skeletal isomerization of n-butenes

The effect upon kinetic behaviour (activity and selectivity) of the physical properties (pore volume distribution) and acidic characteristics (nature of acidic sites and acidic strength distribution) of acidic catalysts in the skeletal isomerization of n-butenes has been studied. The catalysts studied are the following: γ-alumina, alumina modified by introduction of F, Cl and Br, silica–alumina, HZSM-5 zeolite-based catalyst and SAPO-34-based catalyst. It has been proven that the selectivity of acidic catalysts towards the skeletal isomerization of n-butenes is the result of a compromise between pore shape selectivity and intrinsic selectivity of the acidic sites of different strength, this latter property being more significant. Strong acidic sites are needed for the skeletal isomerization, but sites which are too strong produce important amounts of byproducts. A chlorinated alumina is a highly active and selective catalyst for skeletal isomerization. © 1998 SCI.     

Methane Aromatization over Cobalt and Gallium -Impregnated HZSM-5 Catalysts

The influence of the catalyst acidity, the ratio of cobalt in the catalyst on the conversion of methane and the stability were evaluated using a fixed-bed microreactor at atmospheric pressure and at a flow rate of 1500 mL/g h (GHSV 600 h^?1). The reaction was conducted at 973 K and 1023 K over gallium and cobalt -impregnated HZSM-5 catalysts. The 2%Ga–2% Co/HZSM-5 catalyst exhibited remarkable stability with no significant deactivation for 100 h on stream, and yielded a maximum conversion of methane to benzene equal to 9.9%. These catalysts were thoroughly characterized using XRD, N₂ adsorption measurements, TPD of NH₃ and FT-IR. The acidity changes severely affected aromatization, and resulted in drastic modifications in product distribution. From this work, we found that only a small fraction of tetrahedral framework aluminum, which corresponds to the Bronsted acid sites, is sufficient to accomplish the aromatization of the intermediates in methane aromatization reaction, while the superfluous strong Bronsted acid sites, which can be decreased by adding Ga and Co, are shown to be related with the aromatic carbonaceous deposits on the catalysts. After adding Ga and Co the strength of Lewis acid sites of the catalyst increased. But the total amount of the acidity on the catalyst decreased.     

Effects of Colloidal Silica Binder on Catalytic Activity and Adhesion of HZSM-5 Coatings for Structured Reactors

HZSM-5 coating using three colloidal silica binders, acidic col oidal silica (ACS), neutral colloidal silica (NCS) and basic col oidal silica (BCS), was prepared to study the effect of binders on their...     

酸性催化剂催化异丙醇脱水制丙烯反应

对HZSM-5及Zn改性HZSM-5、SAPO-34、MCM-41和磷钨酸负载MCM-41分子筛催化剂进行表征,评价固定床反应器中催化异丙醇脱水反应.Zn改性HZSM-5可有效调节催化剂的酸性,提高催化剂选择性,酸性较弱的SAPO-34与Al2O3质量比为5:1混合组成的SAPO-34催化剂和MCM-41分子筛也表现出...     

n-Pentane Isomerization Over Pt- and Ni–Pt-Promoted Sulfated Zirconia Catalysts Supported on Alumina

Two series of sulfated zirconia catalysts promoted with Pt and Pt–Ni, respectively, were prepared and extruded with different amount of alumina binder (0, 20, 33, and 60 wt%). The catalytic activities of the two series of catalysts, SZPtA and SZNiPtA, were measured for n-pentane isomerization reaction. The reaction reaches its maximum conversion at 20 wt% of alumina for both catalyst series. Adding alumina beyond 20 wt% reduces the overall conversion and modifies the selectivity for both catalysts series from i-C4 towards i-C5 suggesting that the reaction mechanism changed from a monomolecular to a bimolecular one. However, only SZNiPtA catalysts maintain a higher catalytic activity at higher amounts of alumina. Such difference between the two catalyst series can be attributed to the combining effect of Ni and Pt promotion of the SZNiPtA catalysts and not to their acidic properties.     

Enhancing the Production of Light Olefins by Catalytic Cracking of FCC Naphtha over Mesoporous ZSM-5 Catalyst

The enhanced production of light olefins from the catalytic cracking of FCC naphtha was investigated over a mesoporous ZSM-5 (Meso-Z) catalyst. The effects of acidity and pore structure on conversion, yields and selectivity to light olefins were studied in microactivity test (MAT) unit at 600 °C and different catalyst-to-naphtha (C/N) ratios. The catalytic performance of Meso-Z catalyst was compared with three conventional ZSM-5 catalysts having different SiO₂/Al₂O₃ (Si/Al) ratios of 22 (Z-22), 27 (Z-27) and 150 (Z-150). The yields of propylene (16 wt%) and ethylene (10 wt%) were significantly higher for Meso-Z compared with the conventional ZSM-5 catalysts. Almost 90% of the olefins in the FCC naphtha feed were converted to lighter olefins, mostly propylene. The aromatics fraction in cracked naphtha almost doubled in all catalysts indicating some level of aromatization activity. The enhanced production of light olefins for Meso-Z is attributed to its small crystals that suppressed secondary and hydrogen transfer reactions and to its mesopores that offered easier transport and access to active sites.     

Comparison of Activity and Selectivity of SSZ-33 Based Catalyst with other Zeolites in Toluene Disproportionation

SSZ-33 based-catalyst, after modification with Mo and alumina binder, was evaluated in long-run tests in the toluene disproportionation in the presence of hydrogen as a carrier gas. The activity and selectivity of this catalyst were compared with those of ZSM-5 and mesoporous ZSM-5 prepared with the same concentration of Mo and alumina. Formation of the final catalysts decreased the void volume of micropores in order SSZ-33 > ZSM-5 > ZSM-5/Meso. Simultaneously, the concentration of Lewis acid sites increased due to the addition of alumina to the catalyst. The highest toluene conversion was achieved with SSZ-33 catalyst comprising 12-12-10-ring channels, which is the result of high acidity of this zeolite together with increased mass transport through large pores. ZSM-5 zeolite exhibited lower toluene conversion while only a low activity was found for mesoporous ZSM-5 probably due to the limitations of the access to the zeolite channels after modification with alumina.     

高温水蒸汽处理对HZSM-5分子筛催化甲醇制丙烯的影响

考察不同硅铝比的HZSM-5分子筛催化剂和经过高温水蒸汽处理后的HZSM-5分子筛催化剂在甲醇制丙烯反应中的催化性能,考察温度和空速对催化反应的影响。结果表明,随着HZSM-5分子筛硅铝比的增加,产物中丙烯选择性增大,可能是分子筛的酸性降低所致;经过高温水蒸汽处理后的HZSM-5分子筛表面酸性降低,提高了催化剂的催化性能。在反应温度450 ℃和空速1.0 h^-1条件下,600 ℃高温水蒸汽处理后的催化剂HT-600的丙烯选择性从改性前的26.8%提高到33.5%。     

Thermal and catalytic upgrading of a biomass‐derived oil in a dual reaction system

The thermal and catalytic upgrsding of bio‐oil to liquid fuels was studied at atmospheric pressure in a dual reactor system over HZSM‐5, silica‐alumina and a mixed catalyst containing HZSM‐5 and silica‐alumina. This bio‐oil was produced by the rapid thermal processing of the maple wood. In this work, the intent was to improve the catalyst life. Therefore, the first reactor containing no catalyst facilitated thermal cracking of blo‐oil whereas the second reactor containing the desired catalyst upgraded the thermally cracked products. The effects of process variables such as reaction temperature (350°C to 410°C), space velocity (1.8 to 7.2 h^?1) and catalyst type on the amounts and quality of organic liquid product (OLP) were investigated, In the case of HZSM‐5 catalyst, the yield of OLP was maximum at 27.2 wt% whereas the selectivity for aromatic hydrocarbons was maximum at 83 wt%. The selectivities towards aromatics and aliphatic hydrocarbons were highest for mixed and silica‐alumina catalysts, respectively. In all catalyst cases, maximum OLP was produced at an optimum reaction temperature of 370°C in both reactors, and at higher space velocity. The gaseous product consisted of CO and CO₂, and C₁‐C₆ hydrocarbons, which amounted to about 20 to 30 wt% of bio‐oil. The catalysts were deactivated due to coking and were regenerated to achieve their original activity.     

Nano-bonded refractory castables

Calcium aluminate cement (CAC) contents higher than 3 wt% in refractory castables can have some drawbacks in the various processing steps (mainly drying) and also in their refractoriness when in contact with SiO₂. The use of colloidal silica as an alternative binder has been studied by many researchers in recent years and recently reports have also explored the use of colloidal alumina for the same purpose. This article reviews the recent developments in nano-bonded refractory castables focusing on the use of colloidal silica or alumina. In the first part of the paper, a comparison of different binding systems for refractory castables is shown. The benefits of replacing CAC or hydratable alumina by colloidal binders are discussed. In the second part, the advantages of colloidal silica/alumina as a refractory binder are highlighted. Meanwhile, the characterization techniques and functional mechanisms of these binders are presented in order to understand the behavior of these systems. Finally, in the last section, the challenges for suitable use of colloidal binders are discussed and the future direction of nano-structured refractory castables is outlined.     

High efficient mesoporous HZSM-5 nanocatalyst development through desilication with mixed alkaline solution for methanol to olefin reaction

Methanol to olefin (MTO) process is a non-oil route for the light olefins production. We report the mesoporous and high siliceous HZSM-5 nanocatalyst development through the new desilication process including the mixed alkaline solution. The properties of nanocatalysts were characterized using TGA/DTA, XRD, ICP, FE-SEM, BET, FT-IR, and NH₃-TPD techniques. FE-SEM images represent the spherical morphology of parent nanocatalyst including smooth surface. The XRD analysis confirms that applied desilication does not change the typical MFI-type structure of ZSM-5 nanocatalysts. The BET and NH₃-TPD results show that mixed alkaline solution including 40 wt% TPAOH results in the best adjustment of textural (299.7 m²/g) and acidity (strong/weak ratio of 0.21) properties, respectively. The PHZ-NaTP0.4 nanocatalyst represents the highest methanol conversion (99.2%), propylene selectivity (48.3%), C₃ ⁼/C₂ ⁼ molar ratio (7.4) as well as lowest selectivity to C₁–C₄ alkanes (4.6%) for long time on stream (170 h). The low selectivity of light alkanes (C₁–C₄) and high total light olefins (ca. 75%) confirm the stable performance of nanocatalyst. Consequently, the developed PHZ-NaTP0.4 nanocatalyst is a high efficient MTO catalyst and can be candidate for commercial scale up.     

Effects of catalyst acidity and HZSM-5 channel volume on polypropylene cracking

Effects of catalyst acidity and the restricted reaction volume afforded by HZSM-5 on the catalytic cracking of polypropylene are described. Polypropylene cracking by silica—alumina and HZSM-5 catalysts yields olefins as primary volatile products. In addition, HZSM-5 channels restrict carbenium ion rearrangements and facilitate formation of significant amounts of propene and alkyl aromatic volatile products. The higher acidity of sulfated zirconia compared to the other catalysts results in an increase in the frequency of hydride abstractions, resulting in the formation of significant yields of saturated hydrocarbons and organic residue for this catalyst. Primary polypropylene cracking products can be derived from carbenium ion reaction mechanisms. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 341–348, 1998     

Influence of pseudo-boehmite binder modified dealuminated mordenite on Friedel–Crafts alkylation

The influence of pseudo-boehmite binder on the catalytic properties of dealuminated mordenite (MOR) catalyst for Friedel–Crafts alkylation was investigated. Solid-state ²⁷Al MAS NMR spectroscopy, temperature-programmed desorption of ammonia (NH₃-TPD), BET surface area measurement and catalyst particle mechanical strength were used to characterize the catalysts. It was observed that the addition of pseudo-boehmite binder results in improvement in terms of pore size distribution and its mechanical strength. Furthermore, the dredged pore path of MOR was not destroyed although the acid amount and acid type were adjusted properly when the modified MOR was calcinated. Among these catalysts studied, the catalyst bound with 10 wt% pseudo-boehmite binder showed the best catalytic performance in terms of yield and stability, which can be attributed to its maximum medium strong acid amount and its structural properties which is favorable for fast diffusion of products.     

MCM-22沸石催化剂的苯与长链烯烃烷基化性能

用NH3-TPD法研究了4种不同硅铝摩尔比的MCM-22沸石的酸性质,在常压间歇式反应器中考察了它们在苯与长链烯烃烷基化反应中的催化性能,并与HY和HZSM-5沸石催化剂进行了比较。实验结果发现MCM-22的催化活性与其强酸量有一致的关系,与其硅铝摩尔比无对应关系;MCM-22的活性比HY低,但对2-P的选择性远远高于HY,这说明了MCM-22对2-P具有形状选择作用。     

Oxydehydrogenation of propane catalyzed by VSiO cogels: enhancement of the selectivity to propylene by operation under cyclic conditions

The selectivity to propylene in the oxydehydrogenation of propane is improved when the reaction is carried out under cyclic, redox-decoupled conditions rather than under stationary, co-feeding conditions, and using vanadium oxide dispersed in silica as the catalyst. However, the improvement in selectivity is possible only in samples having a V content which is lower than 10 wt% V₂O₅. This points out the importance of having dispersed vanadium oxide to limit the consecutive combustion of propylene.