Metal oxide–zeolite composites in transformation of methanol to hydrocarbons : do iron oxide and nickel oxide matter?

The methanol-to-hydrocarbon (MTH) reaction has received considerable attention as utilizing renewable sources of both value-added chemicals and fuels becomes a number one priority for society. Here, for the first time we report the development of hierarchical zeolites (ZSM-5) containing both iron oxide and nickel oxide nanoparticles. By modifying the iron oxide (magnetite, Fe3O4) amounts, we are able to control the catalyst activity and the product distribution in the MTH process. At the medium Fe3O4 loading, the major fraction is composed of C9–C11 hydrocarbons (gasoline fraction). At the higher Fe3O4 loading, C1–C4 hydrocarbons prevail in the reaction mixture, while at the lowest magnetite loading the major component is the C5–C8 hydrocarbons. Addition of Ni species to Fe3O4–ZSM-5 leads to the formation of mixed Ni oxides (NiO/Ni2O3) positioned either on top of or next to Fe3O4 nanoparticles. This modification allowed us to significantly improve the catalyst stability due to diminishing coke formation and disordering of the coke formed. The incorporation of Ni oxide species also leads to a higher catalyst activity (up to 9.3 g(methanol)/(g(ZSM-5) × h)) and an improved selectivity (11.3% of the C5–C8 hydrocarbons and 23.6% of the C9–C11 hydrocarbons), making these zeolites highly promising for industrial applications

ZnO Particles Stabilized in Polymeric Matrix for Liquid-Phase Methanol Synthesis

ZnO supported on hypercrosslinked polystyrene was developed for liquid-phase methanol synthesis. The synthesized catalyst was characterized using the low-temperature nitrogen physisorption, TEM, XPS, XAS, and CO DRIFT methods. The analysis showed that the catalyst has a high specific surface area (720 m2/g) and is characterized by the micro-mesoporous structure typical of the polymer used. The active phase is represented by ZnO species with a hexagonal wurtzite structure. ZnO-HPS showed high activity, selectivity, and stability in liquid-phase methanol synthesis in comparison with the industrial catalyst. The activity of the proposed catalyst was found to be 1.64 times higher than that of the conventional Cu/ZnO/Al2O3

Thermal behavior of a catalytic packed-Bed Milli-reactor operated under radio frequency heating

An approach for analysis of thermal gradients in a catalytic packed bed milli-reactor operated under radio frequency (RF) heating has been presented. A single-point temperature measurement would cause the misinterpretation of the catalytic activity in an RF-heated reactor, because of the presence of a temperature gradient. For reliable data interpretation, the temperature should be measured at three positions along the reactor length. The temperature profile can be accurately estimated with the exact analytical solution of a one-dimensional (1D) convection and conduction heat-transfer model, and it can also be approximated with a second-order polynomial function. The results revealed that the position of maximum temperature in the catalytic bed shifts toward a downstream location as the flow rate increases. The relative contribution of conduction and convection to the overall heat transport has been discussed. The design criteria for a near-isothermal milli-reactor have been suggested

ZnO Particles Stabilized in Polymeric Matrix for Liquid-Phase Methanol Synthesis

ZnO supported on hypercrosslinked polystyrene was developed for liquid-phase methanol synthesis. The synthesized catalyst was characterized using the low-temperature nitrogen physisorption, TEM, XPS, XAS, and CO DRIFT methods. The analysis showed that the catalyst has a high specific surface area (720 m2/g) and is characterized by the micro-mesoporous structure typical of the polymer used. The active phase is represented by ZnO species with a hexagonal wurtzite structure. ZnO-HPS showed high activity, selectivity, and stability in liquid-phase methanol synthesis in comparison with the industrial catalyst. The activity of the proposed catalyst was found to be 1.64 times higher than that of the conventional Cu/ZnO/Al2O3

Amino-Modified Silica as Effective Support of the Palladium Catalyst for 4-Nitroaniline Hydrogenation

The article describes the synthesis of aminoorgano-functionalized silica as a prospective material for catalysis application. The amino groups have electron donor properties which are valuable for the metal chemical state of palladium. Therefore, the presence of electron donor groups is important for increasing catalysts’ stability. The research is devoted to the investigation of silica amino-modified support influence on the activity and stability of palladium species in 4-nitroaniline hydrogenation process. A series of catalysts with different supports such as SiO2, SiO2-C3H6-NH2 (amino-functionalized silica), γ-Al2O3 and activated carbon were studied. The catalytic activity was studied in the hydrogenation of 4-nitroaniline to 1,4-phenylenediamine. The catalysts were characterized by scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and chemisorption of hydrogen by the pulse technique. The 5 wt.% Pd/SiO2-C3H6-NH2 catalyst exhibited the highest catalytic activity for 4-nitroaniline hydrogenation with 100% conversion and 99% selectivity with respect to 1,4-phenylenediamine

Highly Selective CO₂ Hydrogenation to Methanol over Complex In/Co Catalysts: Effect of Polymer Frame

The growing demand for new energy sources governs the intensive research into CO2 hydrogenation to methanol, a valuable liquid fuel. Recently, indium-based catalysts have shown promise in this reaction, but they are plagued by shortcomings such as structural instability during the reaction and low selectivity. Here, we report a new strategy of controlling the selectivity and stability of bimetallic magnetically recoverable indium-based catalysts deposited onto a solid support. This was accomplished by the introduction of a structural promoter: a branched pyridylphenylene polymer (PPP). The selectivity of methanol formation for this catalyst reached 98.5%, while in the absence of PPP, the catalysts produced a large amount of methane, and the selectivity was about 70.2%. The methanol production rate was higher by a factor of twelve compared to that of a commercial Cu-based catalyst. Along with tuning selectivity, PPP allowed the catalyst to maintain a high stability, enhancing the CO2 sorption capacity and the protection of In against sintering and over-reduction. A careful evaluation of the structure–activity relationships allowed us to balance the catalyst composition with a high level of structural control, providing synergy between the support, magnetic constituent, catalytic species, and the stabilizing polymer layer. We also uncovered the role of each component in the ultimate methanol activity and selectivity

Cr-Zn/Ni-Containing Nanocomposites as Effective Magnetically Recoverable Catalysts for CO₂ Hydrogenation to Methanol: The Role of Metal Doping and Polymer Co-Support

CO2 hydrogenation to methanol is an important process that could solve the problem of emitted CO2 that contributes to environmental concern. Here we developed Cr-, Cr-Zn-, and Cr-Ni-containing nanocomposites based on a solid support (SiO2 or Al2O3) with embedded magnetic nanoparticles (NPs) and covered by a cross-linked pyridylphenylene polymer layer. The decomposition of Cr, Zn, and Ni precursors in the presence of supports containing magnetic oxide led to formation of amorphous metal oxides evenly distributed over the support-polymer space, together with the partial diffusion of metal species into magnetic NPs. We demonstrated the catalytic activity of Cr2O3 in the hydrogenation reaction of CO2 to methanol, which was further increased by 50% and 204% by incorporation of Ni and Zn species, respectively. The fine intermixing of metal species ensures an enhanced methanol productivity. Careful adjustment of constituent elements, e.g., catalytic metal, type of support, presence of magnetic NPs, and deposition of hydrophobic polymer layer contributes to the synergetic promotional effect required for activation of CO2 molecules as well. The results of catalytic recycle experiments revealed excellent stability of the catalysts due to protective role of hydrophobic polymer

Comparison of methanol to gasoline conversion in one-step, two-step, and cascade mode in the presence of H-ZSM-5 zeolite

In this report, three technological modes for methanol-to-gasoline reaction in the presence of H-ZSM-5 catalyst are compared: (i) direct methanol transformation to hydrocarbons; (ii) two-step (methanol-dimethyl ether-hydrocarbons); and (iii) cascade pathway. Light hydrocarbon gases (methane, ethylene, propylene, and isobutene) and liquid aromatic hydrocarbons (benzene, toluene, xylene, cresol, durol, naphthalene, methylnaphthalene, ethyl naphthalene, isopropyl naphthalene, methyl isopropyl naphthalene, etc.) were found to be the main reaction products. The experimental results showed that the classical two-step methanol to gasoline (MTG) process nowadays remains the most effective for gasoline-range hydrocarbons production, while one-step and cascade schemes require further investigation and the development of reactor systems as well as the operating conditions. The product distribution of MTG synthesis after 120 h on stream in the case of two-step mode was found to be the following: liquid C6–C8 hydrocarbons – 23%; C1–C5 gaseous products – 65%; heavy C9–C12 hydrocarbons – 10%

Metal-Ion Distribution and Oxygen Vacancies That Determine the Activity of Magnetically Recoverable Catalysts in Methanol Synthesis

Here, we report on the development of novel Zn-, Zn–Cr-, and Zn–Cu-containing catalysts using magnetic silica (Fe₃O₄–SiO₂) as the support. Transmission electron microscopy, powder X-ray diffraction, and X-ray photoelectron spectroscopy (XPS) showed that the iron oxide nanoparticles are located in mesoporous silica pores and the magnetite (spinel) structure remains virtually unchanged despite the incorporation of Zn and Cr. According to XPS data, the Zn and Cr species are intermixed within the magnetite structure. In the case of the Zn–Cu-containing catalysts, a separate Cu₂O phase was also observed along with the spinel structure. The catalytic activity of these catalysts was tested in methanol synthesis from syngas (CO + H₂). The catalytic experiments showed an improved catalytic performance of Zn- and Zn–Cr-containing magnetic silicas compared to that of the ZnO–SiO₂ catalyst. The best catalytic activity was obtained for the Zn–Cr-containing magnetic catalyst prepared with 1 wt % Zn and Cr each. X-ray absorption spectroscopy demonstrated the presence of oxygen vacancies near Fe and Zn in Zn-containing, and even more in Zn–Cr-containing, magnetic silica (including oxygen vacancies near Cr ions), revealing a correlation between the catalytic properties and oxygen vacancies. The easy magnetic recovery, robust synthetic procedure, and high catalytic activity make these catalysts promising for practical applications