Search Results (10)

The hydro-upgrading reaction behavior of model compound 1-hexene and FCC middle gasoline was investigated using a fixed-bed hydrogenation microreactor with a prepared La-Ni-Zn/H-ZSM-5 catalyst. The catalyst was prepared by wetness impregnation method, using hydrothermal treated H-ZSM-5 zeolite blended with alumina as the support, and La, Ni, Zn as the active metals. The reaction tests were carried out at 300–380 °C, 1.0 MPa, 1.5–3.0 h⁻¹ (LSHV), and 300:1 v/v (H₂/oil). Analyzing the changes in hydrocarbon components before and after hydro-upgrading elucidated the mechanistic pathways of olefin hydroisomerization and hydroaromatization. Based on these findings, a seven-lump kinetic model was established for the FCC middle gasoline hydro-upgrading process. Given the diversity and complexity of reaction products, they were grouped into seven lumps: normal paraffins, isoparaffins, linear olefins, branched olefins, cycloolefins, naphthenes, and aromatics. Kinetic parameters were estimated using the Levenberg–Marquardt algorithm and validated against experimental data. The results showed that the conversion of naphthenes to aromatics exhibited the highest activation energy and pre-exponential factor, resulting in the largest reaction rate increase within the 320–380 °C range. The model accurately predicted the product yields of FCC gasoline hydro-upgrading, with a relative error of less than 5%. These findings provide valuable guidance for the optimization, design, and operation of FCC gasoline hydro-upgrading units, as well as for catalyst development, with the aim of improving process efficiency and fuel quality. Full article

Aromatics assume a paramount role as indispensable organic chemical feedstock within diverse industrial domains. Simultaneously, the global aromatics market is scarce, particularly with the exorbitant demand for high-value aromatics. Generating aromatics via coal-based methanol and low-carbon hydrocarbon coupling reactions has become a novel green and sustainable development trajectory. In this study, HZSM-5 catalysts featuring different Si/Al ratios and active metal-functionalized modifications were utilized to explore the aromatization effect in light of the Si/Al ratio, types of active components, and metal-loading content in a fixed-bed reactor. The outcomes were that the conversion ratios for methanol and n-pentane attained 99.9% and 83.1%, respectively. Remarkably, an oil phase yield of 32.1% was accomplished, along with an aromatic content of approximately 74.2%, while xylene selectivity reached approximately 37.6% for the 1.0%-ZnO/ZSM-5 (50) catalyst. Ultimately, a reaction mechanism for the coupling of methanol and n-pentane to yield aromatics using a 1.0%-ZnO/ZSM-5(50) catalyst is postulated. Full article

During the methanol-to-aromatics (MTA) process, a large amount of water is generated, while the influence and mechanism of water on the activity and selectivity of the light olefin aromatization reaction are still unclear. Therefore, a study was conducted to systematically investigate the effects of water on the reactivity and the product distribution in ethylene aromatization using infrared spectroscopy (IR), intelligent gravitation analyzer (IGA), and X-ray absorption fine structure (XAFS) characterizations. The results demonstrated that the presence of water reduced ethylene conversion and aromatic selectivity while increasing hydrogen selectivity at the same contact time. This indicated that water had an effect on the reaction pathway by promoting the dehydrogenation reaction and suppressing the hydrogen transfer reaction. A detailed analysis using linear combination fitting (LCF) of Zn K-edge X-ray absorption near-edge spectroscopy (XANES) on Zn/HZSM-5 catalysts showed significant variations in the state of existence and the distribution of Zn species on the deactivated catalysts, depending on different reaction atmospheres and water contents. The presence of water strongly hindered the conversion of ZnOH⁺ species, which served as the active centers for the dehydrogenation reaction, to ZnO on the catalyst. As a result, the dehydrogenation activity remained high in the presence of water. This study using IR and IGA techniques revealed that water on the Zn/HZSM-5 catalyst inhibited the adsorption of ethylene on the zeolite, resulting in a noticeable decrease in ethylene conversion and a decrease in aromatic selectivity. These findings contribute to a deeper understanding of the aromatization reaction process and provide data support for the design of efficient aromatization catalysts. Full article

Investigating the distribution of different Zn species on Zn-containing zeolite catalysts is crucial for identifying the active sites and establishing the relationship between the catalyst’s structure and its activity in the process of ethylene aromatization. By utilizing X-ray absorption near edge spectra (XANES) of various reference samples, this study employed linear combination fitting (LCF) analysis on XANES spectra of real samples to accurately measure the changes in the distribution of Zn species in Zn-containing HZSM-5 zeolites under different Zn sources and loadings. The results showed that ZnOH⁺, ZnO clusters, and ZnO crystalline structures coexist in Zn/HZSM-5 catalysts prepared through physical mixing and incipient wet impregnation methods. A similar trend was observed for catalysts prepared using different methods, with an increase in Zn content resulting in a decrease in the proportion of ZnOH⁺ and a significant increase in the amount of larger ZnO crystals. Furthermore, ZnO clusters were confined within the zeolite pores. The findings of this study established a direct correlation between the amount of ZnOH⁺ determined through LCF analysis and both the rate of hydrogen production and the rate of aromatics formation, providing strong evidence for the catalytic role of ZnOH⁺ as an active center for dehydrogenation, which plays a key role in promoting the formation of aromatics. The method of LCF analysis on XANES spectra allows for the determination of the local structure of Zn species, facilitating a more precise analysis based on the distribution of these species. This method not only provides detailed information about the Zn species but also enhances the accuracy of the overall analysis. Full article

Catalytic cracking of bio-oil, conducted at atmospheric pressure without hydrogen supply, is a cost-effective and versatile approach for the targeted synthesis of biofuels and platform chemicals. The conversion of raw bio-oil follows intricate reaction pathways strongly influenced by the catalyst properties. In this work, we explore the use of various transition metals (Cr, Fe, and Zn) to modify the properties of HZSM-5 zeolite and assess their impact on the catalytic cracking of real raw bio-oil feedstock. The effect of metal loading on physical and chemical characteristics of metal-doped zeolite catalysts was studied through XRD, XRF, N₂ physisorption, NH₃-TPD, FTIR, H₂-TPR. The behavior of each catalyst was evaluated in a continuous two-step catalytic cracking system (TS-CC) operating at 450 °C and space-time 0.7 g_catalysth/g_feed. The results highlight the importance of carefully selecting active metal species to optimize the performance of HZSM-5 in the catalytic cracking of bio-oil. Cr and Fe were found to be effective metals in increasing the selectivity of C₂–C₄ olefins in the gas product and mono-aromatics in the hydrocarbon liquid product, whereas the Zn-doped catalyst exhibits poor activity compared to bulk zeolite. Furthermore, a significant impact of the metal oxidation state on catalytic activity was observed, with reduced metals promoting the formation of H₂, CO, and CO₂ at the expense of hydrocarbon production. Full article

It is important to clarify the distribution of pyrolysis products from lignocellulosic biomass for its thermal transformation to produce high-quality bio-oil. Influences of the reaction temperature and catalysts on the pyrolysis product distribution from aspen wood (AW) and rice husk (RH) were studied by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). The difference in components from the lignocellulosic biomass results in different pyrolysis characteristics of the biomass raw materials. The reaction temperature significantly influences the product distribution from AW and RH pyrolysis. In all AW catalysis experiments, acids (8.35%), ketones (3.79%), phenols (4.73%), and esters (1.50%) have the lowest content while carbohydrates (48.75%) demonstrate the highest content when taking zinc chloride (ZnCl₂) as the catalyst; the HZSM-5 molecular sieve (HZSM-5) promotes the generation of esters (7.97%) and N-compounds (22.43%) while inhibiting production of aldehydes (2.41%); addition of an MCM-41 molecular sieve (MCM-41) is conducive to increasing the contents of aldehydes (21.29%), furans (5.88%), ketones (22.30%), acids (20.46%), and hydrocarbons (4.85%), while reducing the contents of alcohols (0) and carbohydrates (0). In all RH catalysis experiments, the addition of ZnCl₂ helps increase the content of carbohydrates (39.16%) and decrease the contents of ketones (3.89%), phenols (5.20%), alcohols (2.34%), esters (1.13%), and N-compounds (3.09%); when applying HZSM-5 as the catalyst, hydrocarbons (18.28%) and alcohols (6.66%) reach their highest content while acids (13.21%) have the lowest content; MCM-41 promotes the generation of aldehydes (25.33%) and furans (5.55%) while inhibiting that of carbohydrates (1.42%). Full article

A systematic study of the comparative performances of different metal-impregnated HZSM-5 catalysts (Zn, Ga, Mo, Co, and Zr) for propane conversion is presented. The physicochemical properties of catalysts were characterized by means of XRD, BET, SEM, TEM, FTIR, XPS, ²⁷Al MAS NMR, NH₃-TPD and Py-FTIR. It was found that the acidities of the catalysts were significantly influenced by loading metal. More specifically, Mo-, Co- or Zr-modified catalysts showed a large metal size and low acidic density, resulting high olefin selectivity, while Zn- or Ga-modified catalysts maintained their small metal size and acidic density, and mainly reduced B/L due to the Lewis acid sites created by Zn or Ga species, resulting in high aromatics selectivity. Experimental results also showed that there is a balance between metals size and medium and strong acidity on propane conversion. Moreover, based on the different acidity of metal-modified HZSM-5 catalysts, the mechanism of propane conversion was also discussed. Full article

The performance of bifunctional hybrid catalysts based on phosphotungstic acid (H₃PW₁₂O₄₀, HPW) supported on TiO₂ combined with Cu-ZnO(Al) catalyst in the direct synthesis of dimethyl ether (DME) from syngas has been investigated. We studied the effect of the HPW loading on TiO₂ (from 1.4 to 2.7 monolayers) on the dispersion and acid characteristics of the HPW clusters. When the concentration of the heteropoliacid is slightly higher than the monolayer (1.4 monolayers) the acidity of the clusters is perturbed by the surface of titania, while for concentration higher than 1.7 monolayers results in the formation of three-dimensional HPW nanocrystals with acidity similar to the bulk heteropolyacid. Physical hybridization of supported heteropolyacids with the Cu-ZnO(Al) catalyst modifies both the acid characteristics of the supported heteropolyacids and the copper surface area of the Cu-ZnO(Al) catalyst. Hybridization gives rise to a decrease in the copper surface area and the disappearance of the strong acidic sites typical of HPW nanocrystals, showing all hybrids similar acid sites of weak or medium strength. The activity of the hybrids was tested for direct DME synthesis from syngas at 30 bar and 250 °C; only the hybrids with HPW loading higher than 1.4 monolayers showed activity for the direct synthesis of DME, showing that the sample loaded with 2.7 monolayers of heteropolyacid had higher activity than the reference hybrid representative of the most widely applied catalysts based on the combination of Cu-ZnO(Al) with HZSM-5. In spite of the high activity of the hybrids, they show a moderate loss in the DME production with TOS that denotes some kind of deactivation of the acidity function under reaction conditions. Full article

Nano-sized HZSM-5 (n-HZSM-5) was synthesized and applied in the aromatization of glycerol. The effects of additives (carboxymethylcellulose sodium, NaCl, sodium alginate, etc.) on the chemical and physic properties of n-HZSM-5 during preparation were investigated. Metal modification was also investigated based on the synthesized n-HZSM-5. The results showed that the addition of carboxymethylcellulose sodium (CMC-Na), NaCl and sodium alginate (SA) led to forming smaller sizes of HZSM-5 and promoted the acid amounts of the catalysts, which increased its catalytic activities for obtaining BTX. The highest BTX yield of ~35% was obtained by SA derived n-HZSM-5, and the life of the catalyst were both obviously promoted by the additives with a highest of ~11 h by γ-(2,3-epoxypropoxy)propytrimethoxysilane (KH-560) derived n-HZSM-5. BTX yields could be improved by 40%by the addition of Zn and Cd in n-HZSM-5 while having little effect on the catalyst life. Full article

A series of defective ZSM-5 zeolites (~300 nm, SiO₂/Al₂O₃ ratio of 55, 100, 480 and 950) were systematically studied by XRD, SEM, ²⁹Si MAS NMR, argon physisorption, NH₃-TPD and FT-IR technologies. The nature, the amount and the accessibility of the acid sites of defective ZSM-5 zeolites are greatly different from reported ZSM-5 zeolites with a perfect crystal structure. The Brønsted acid sites (Si(OH)Al) with strong acid strength and the Brønsted acid sites (hydroxyl nests) with weak acid strength co-existed over defective ZSM-5 zeolites, which leads to a unique catalytic function. Zn(C₂H₅)₂ was grafted onto defective ZSM-5 zeolites through the chemical liquid deposition (CLD) method. Interestingly, FT-IR spectroscopic studies found that Zn(C₂H₅)₂ was preferentially grafted on the hydroxyl nests with weak acid strength rather than the Si(OH)Al groups with strong acid strength over different defective ZSM-5 zeolites. In particular, home-built operando dual beam FTIR-MS was applied to study the catalytic performance of Zn species located in different sites of defective ZSM-5 zeolites under real n-hexane transformation conditions. Results show that Zn species grafted over hydroxyl nests obtain better dehydrogenative aromatization performance than Zn species over Si(OH)Al groups. This study provides guidance for the rational design of highly efficient alkane dehydrogenative aromatization catalysts. Full article