Methanol Dehydration to Dimethyl Ether on Zr-Loaded P-Containing Mesoporous Activated Carbon Catalysts

Palomo, José; Rodríguez-Mirasol, José; Cordero, Tomás

doi:10.3390/ma12132204

Cited by 24 publications

(26 citation statements)

References 60 publications

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“…Water has been reported to compete with methanol for the active sites of the catalyst, causing a decay in DME production [30,[59][60][61]. The inhibitory effect of water is relevant in the experimental conditions reported here, as its concentration is similar to the concentration of DME observed in this work.…”

Section: Effect Of Inlet Water Vaporsupporting

confidence: 64%

“…The impregnated sample was then dried at 120 • C overnight and heated at 250 • C for 2 h, in a muffle furnace. A more detailed description of the catalyst preparation process can be found elsewhere [30].…”

Section: Catalyst Preparationmentioning

confidence: 99%

“…This Zr-loaded P-containing biomass-derived catalyst was already tested at temperatures below 400 • C for the methanol to DME (MTD) reaction (0.02 atm CH3OH and space time of 75 g cat •s/mmol CH3OH ) [30]. This catalyst showed a stable and selective DME production for more than 24 h. However, its performance at higher temperatures, where the methanol conversion is very high (100%), closer to that of the industrial process, was evaluated in this work.…”

Section: Catalyst Performancementioning

confidence: 99%

“…To overcome this problem, zirconium was added to those P-containing activated carbons, obtaining surface zirconium phosphate species [28,29]. The latter catalyst achieved a stable 50% yield to DME for more than 72 h at 350 • C, without the release of any other byproducts [30]. However, when the temperatures were higher, similar to those used in industrial synthesis, a certain loss of activity with time on stream (TOS) can be detected.…”

Section: Introductionmentioning

confidence: 99%

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A Kinetic Model Considering Catalyst Deactivation for Methanol-to-Dimethyl Ether on a Biomass-Derived Zr/P-Carbon Catalyst

et al. 2022

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A Zr-loaded P-containing biomass-derived activated carbon (ACPZr) has been tested for methanol dehydration between 450 and 550 °C. At earlier stages, methanol conversion was complete, and the reaction product was mainly dimethyl ether (DME), although coke, methane, hydrogen and CO were also observed to a lesser extent. The catalyst was slowly deactivated with time-on-stream (TOS), but maintained a high selectivity to DME (>80%), with a higher yield to this product than 20% for more than 24 h at 500 °C. A kinetic model was developed for methanol dehydration reaction, which included the effect of the inhibition of water and the deactivation of the catalyst by coke. The study of stoichiometric rates pointed out that coke could be produced through a formaldehyde intermediate, which might, alternatively, decompose into CO and H2. On the other hand, the presence of 10% water in the feed did not affect the rate of coke formation, but produced a reduction of 50% in the DME yield, suggesting a reversible competitive adsorption of water. A Langmuir–Hinshelwood reaction mechanism was used to develop a kinetic model that considered the deactivation of the catalyst. Activation energy values of 65 and 51 kJ/mol were obtained for DME and methane production in the temperature range from 450 °C to 550 °C. On the other hand, coke formation as a function of time on stream (TOS) was also modelled and used as the input for the deactivation function of the model, which allowed for the successful prediction of the DME, CH4 and CO yields in the whole evaluated TOS interval.

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Section: Effect Of Inlet Water Vaporsupporting

confidence: 64%

Section: Catalyst Preparationmentioning

confidence: 99%

Section: Catalyst Performancementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

A Kinetic Model Considering Catalyst Deactivation for Methanol-to-Dimethyl Ether on a Biomass-Derived Zr/P-Carbon Catalyst

et al. 2022

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“…The surface chemistry of DES/ H 3 PO 4 -600 2:3 was further analyzed using XPS Kratos Axis UltraDLD with ejected photoelectron having a monochromated beam Al Kα X-ray energy source (1486.7 eV). The resulting spectra were referenced by the C1 (graphitic carbon) peak occurring at 284.6 eV (Palomo et al 2019) using the software package (XPSPEAK41). TGA was conducted using thermogravimetric analyzer (STA600 Perkin-Elmer) over a temperature range of 0-900 °C under nitrogen flow at heating rate of 10 °C/min.…”

Section: Adsorbent Characterizationmentioning

confidence: 99%

Pb(II) removal in water via adsorption onto deep eutectic solvent fabricated activated carbon

et al. 2021

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In our current work, we have established a novel approach in the synthesis of a new adsorbent by using choline chloride and urea (DES)/orthophosphoric acid (H3PO4) as our activating agent and palm kernel shell (PKS) as our precursor. The resulting activated carbon (DES/H3PO4-6002:3) was used to adsorb Pb(II) from aqueous solution. Characterization of DES-H3PO4-6002:3 by nitrogen adsorption/desorption isotherm measurements, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA) demonstrated good micropores structure and high surface area that makes DES/H3PO4-600 2:3 a suitable alternative for liquid phase adsorption. The fundamental batch experiment of DES/H3PO4-600 2:3 was investigated by different parameters (such as concentration, pH, temperature and absorbent dose). The results obtained indicated that Langmuir model and pseudo-second-order equation best fit the data, indicating that the adsorption was controlled by chemical reaction and monolayer uptake. In addition, the fabrication of DES/H3PO4 AC exhibits good potential for Pb(II) ions uptake, including its high adsorption capacity (97.1 mg/g) and good recyclability. The future potential of this works lies in the identification of alternatives to environmental benign synthesis AC and reuse of Pb(II) ion–laden biosorbent after heavy metal uptake.

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Promoted catalytic performance of sugarcane bagasse ash supported by γ‐alumina as efficient, stable, and ecofriendly catalyst for dehydration of methanol to dimethyl ether

Said,

Goda,

Abd El‐Wahab

et al. 2024

Asia-Pacific J Chem Eng

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The aim of this study was to use different proportions (1% to 20% by weight) of γ‐alumina to modify sugarcane bagasse ash (SCBA) for the production of dimethyl ether (DME) through the dehydration of methyl alcohol. A simple precipitation method was utilized to fabricate (1–20 wt.%) Al2O3/SCBA catalysts. X‐ray fluorescence, X‐ray diffraction, Fourier‐transform infrared spectroscopy, transmission electron microscopy, and N2 sorption were used to explore the structural, spectroscopic, morphological, and textural features. The XRD pattern of Al2O3/SCBA catalysts showed a new peak that corresponded to the formation of γ‐Al2O3. In addition, the average crystallite sizes of pure SCBA and 10% and 20%Al2O3/SCBA catalysts were calculated and found to be 20.1, 21.6, and 22.6 nm, respectively. To evaluate the acidity of these catalysts, the dehydration of isopropyl alcohol and the chemisorption of basic probe molecules were employed. The acidity test results displayed that these catalysts have weak to moderate acidic sites. The 10% Al2O3/SCBA catalyst calcined at 400°C showed high efficiency for the conversion of methyl alcohol to DME, attaining 89% conversion with 100% selectivity. This observation can be attributed to the even distribution of active sites and the acid–base equilibrium on the surface. Moreover, its catalytic activity and selectivity remain unchanged over a continuous 2‐week operation without coke formation, demonstrating its extremely high stability. A strong correlation was observed between the catalytic activity and both the surface area and acidity of the catalysts.

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Methanol Dehydration to Dimethyl Ether on Zr-Loaded P-Containing Mesoporous Activated Carbon Catalysts

Cited by 24 publications

References 60 publications

A Kinetic Model Considering Catalyst Deactivation for Methanol-to-Dimethyl Ether on a Biomass-Derived Zr/P-Carbon Catalyst

A Kinetic Model Considering Catalyst Deactivation for Methanol-to-Dimethyl Ether on a Biomass-Derived Zr/P-Carbon Catalyst

Pb(II) removal in water via adsorption onto deep eutectic solvent fabricated activated carbon

Promoted catalytic performance of sugarcane bagasse ash supported by γ‐alumina as efficient, stable, and ecofriendly catalyst for dehydration of methanol to dimethyl ether

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