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

Materials ◽  
2022 ◽  
Vol 15 (2) ◽  
pp. 596
Author(s):  
Javier Torres-Liñán ◽  
Ramiro Ruiz-Rosas ◽  
Juana María Rosas ◽  
José Rodríguez-Mirasol ◽  
Tomás Cordero

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.

2020 ◽  
Vol 10 (24) ◽  
pp. 9016
Author(s):  
Ibrahim A. Al-Hawas ◽  
Salah A. Hassan ◽  
Hany M. AbdelDayem

In this work, various physicochemical characteristics, e.g., surface properties and mineralogical compositions, of five clays collected from different sites in the Al-Hasa oasis in Saudi Arabia have been investigated. Analysis of the mineralogical compositions of the clays in the study by X-ray diffraction indicated the coexistence of palygorskite, montmorillonite, illite, kaolinite, chlorite, calcite and quartz in different percentages. Thermogravimetric analysis indicated that all studied clays exhibited dehydroxylation temperatures higher than 470 °C. On the other hand, pore size distribution analysis of clays from N2 adsorption indicated the presence of micro- and narrow mesopores (of 1.3–2.8 nm). Furthermore, the capability of the different clays for removal of Pb (II) from aqueous solution has been studied. The adsorption process was described through the Langmuir, Freundlich, Temkin and Dubinin–Radushkevich models. The Langmuir model was the most suitable compared to the other models in the case of palygorskite- and montmorillonite-rich clays. However, the Temkin model better represented the adsorption process of Pb (II) on calcite-rich clay. The clay sample with 61.0 wt% of palygorskite was found to be the most effective at removing Pb (II), with a maximum removal capacity of 74.07 mg/g at pH 6, with a contact time of 6 h and at 25 °C. Generally, the adsorption mechanism of lead over all the studied clays followed the pseudo-second-order kinetics. On the other hand, the catalytic activity of clays in the study has been tested in methanol conversion. The acidic clays, those containing high amounts of montmorillonite, showed higher selectivity to ethylene, viz., 78.9%, with a methanol conversion of 39.1% at 350 ° C and 0.1 MPa.


Materials ◽  
2020 ◽  
Vol 13 (23) ◽  
pp. 5577
Author(s):  
Enrico Catizzone ◽  
Emanuele Giglio ◽  
Massimo Migliori ◽  
Paolo C. Cozzucoli ◽  
Girolamo Giordano

The synthesis of dimethyl ether (DME) is an important step in the production of chemical intermediate because it is possible to prepare it by direct hydrogenation of CO2. This paper reports the effect of different zeolitic frameworks (such as: BEA, EUO, FER, MFI, MOR, MTW, TON) on methanol conversion, DME selectivity and catalyst deactivation. The effect of crystal size, Si/Al ratio and acidity of the investigated catalysts have been also studied. Finally, the kinetic parameters (such as: ∆H, ∆S and ∆G) have been evaluated together with pre-exponential factor and activation energy for catalysts with FER and MFI structure topology.


2014 ◽  
Vol 931-932 ◽  
pp. 17-21
Author(s):  
Nattaporn Chaba ◽  
Sutasinee Neramittagapong ◽  
Arthit Neramittagapong

Dimethyl Ether (DME) an alternative fuel was synthesized by methanol dehydration over the silica-based catalysts. Silica extracted from both rice husk (A) and rice-husk ash (B) was used as the precursors for preparing the catalysts. The SiO2/Al2O3 and the SAPO catalysts prepared from that silica were analyzed using X-ray diffraction (XRD), N2 adsorption (BET surface area), X-ray fluorescence (XRF), NH3 temperature-programmed desorption (NH3-TPD), and thermal gravimetric analysis (TGA). The effects of reaction temperature on the methanol selectivity and conversion to dimethyl ether were investigated. The methanol dehydration reactions were carried out in a packed-bed reactor at the reaction temperature of 250-350°C. DME was the major product and formed with selectivity of 57% over SAPO-B. An increasing of the reaction temperatures resulted in the enhancing of methanol conversion. The highest methanol conversion of 93% was achieved at 325°C. The method of silica extraction had an effect on the selectivity to DME due to the higher BET surface area.


Materials ◽  
2019 ◽  
Vol 12 (13) ◽  
pp. 2204 ◽  
Author(s):  
José Palomo ◽  
José Rodríguez-Mirasol ◽  
Tomás Cordero

Activated carbons have been prepared by the chemical activation of olive stones with phosphoric acid and loaded with Zr. The addition of Zr to the phosphorus-containing activated carbons resulted in the formation of zirconium phosphate surface groups. Gas phase methanol dehydration has been studied while using the prepared Zr-loaded P-containing activated carbons as catalysts. Carbon catalysts showed high steady-state methanol conversion values, which increased with Zr loading up to a limit that was related to P content. The selectivity towards dimethyl ether was higher than 95% for all Zr loadings. Zirconium phosphate species that were present on catalysts surface were responsible for the catalytic activity.


2014 ◽  
Vol 931-932 ◽  
pp. 42-46 ◽  
Author(s):  
Watcharakorn Pranee ◽  
Pornsawan Assawasaengrat ◽  
Arthit Neramittagapong ◽  
Sutasinee Neramittagapong

The synthesis of dimethyl ether via methanol dehydration has been carried out over untreated-diatomite catalyst (DM) and hydrochloric acid modified treatment on diatomite catalyst (DMHC). The reactions were carried out in a fixed-bed reactor. The effects of hydrochloric acid modifications of diatomite on its catalytic performance were studied. The characterization such as XRD, SEM, FT-IR and FT-Raman had no deformation after HCl-modified treatment on catalysts. DMHC catalyst apparently gave the higher methanol conversion rate than DM due to the acidity while the selectivity of dimethyl ether from 250 to 350°C was slightly changed. The acidity was depended upon Al(IV) ions; nevertheless, both Al(V) and Al(VI) were affected and hence increasing the basic active sites. Not only was the competitively catalytic methanol dehydrogenation preferred with basic condition but also methanol-blocking water molecule interaction was the unwanted reaction. In this investigation, the chemical-bond arrangements of silicon and aluminium ions were proposed with solid MAS/NMR. The DMHC catalyst exhibited better DME yield than the DM catalyst, and it could be used as a selective catalyst for DME synthesis from methanol.


1999 ◽  
Vol 173 ◽  
pp. 249-254
Author(s):  
A.M. Silva ◽  
R.D. Miró

AbstractWe have developed a model for theH2OandOHevolution in a comet outburst, assuming that together with the gas, a distribution of icy grains is ejected. With an initial mass of icy grains of 108kg released, theH2OandOHproductions are increased up to a factor two, and the growth curves change drastically in the first two days. The model is applied to eruptions detected in theOHradio monitorings and fits well with the slow variations in the flux. On the other hand, several events of short duration appear, consisting of a sudden rise ofOHflux, followed by a sudden decay on the second day. These apparent short bursts are frequently found as precursors of a more durable eruption. We suggest that both of them are part of a unique eruption, and that the sudden decay is due to collisions that de-excite theOHmaser, when it reaches the Cometopause region located at 1.35 × 105kmfrom the nucleus.


Author(s):  
A. V. Crewe

We have become accustomed to differentiating between the scanning microscope and the conventional transmission microscope according to the resolving power which the two instruments offer. The conventional microscope is capable of a point resolution of a few angstroms and line resolutions of periodic objects of about 1Å. On the other hand, the scanning microscope, in its normal form, is not ordinarily capable of a point resolution better than 100Å. Upon examining reasons for the 100Å limitation, it becomes clear that this is based more on tradition than reason, and in particular, it is a condition imposed upon the microscope by adherence to thermal sources of electrons.


Author(s):  
Clifford S. Rainey

The spatial distribution of V and Ni deposited within fluidized catalytic cracking (FCC) catalyst is studied because these metals contribute to catalyst deactivation. Y zeolite in FCC microspheres are high SiO2 aluminosilicates with molecular-sized channels that contain a mixture of lanthanoids. They must withstand high regeneration temperatures and retain acid sites needed for cracking of hydrocarbons, a process essential for efficient gasoline production. Zeolite in combination with V to form vanadates, or less diffusion in the channels due to coke formation, may deactivate catalyst. Other factors such as metal "skins", microsphere sintering, and attrition may also be involved. SEM of FCC fracture surfaces, AEM of Y zeolite, and electron microscopy of this work are developed to better understand and minimize catalyst deactivation.


Author(s):  
K.H. Westmacott

Life beyond 1MeV – like life after 40 – is not too different unless one takes advantage of past experience and is receptive to new opportunities. At first glance, the returns on performing electron microscopy at voltages greater than 1MeV diminish rather rapidly as the curves which describe the well-known advantages of HVEM often tend towards saturation. However, in a country with a significant HVEM capability, a good case can be made for investing in instruments with a range of maximum accelerating voltages. In this regard, the 1.5MeV KRATOS HVEM being installed in Berkeley will complement the other 650KeV, 1MeV, and 1.2MeV instruments currently operating in the U.S. One other consideration suggests that 1.5MeV is an optimum voltage machine – Its additional advantages may be purchased for not much more than a 1MeV instrument. On the other hand, the 3MeV HVEM's which seem to be operated at 2MeV maximum, are much more expensive.


2005 ◽  
Vol 19 (3) ◽  
pp. 129-132 ◽  
Author(s):  
Reimer Kornmann

Summary: My comment is basically restricted to the situation in which less-able students find themselves and refers only to literature in German. From this point of view I am basically able to confirm Marsh's results. It must, however, be said that with less-able pupils the opposite effect can be found: Levels of self-esteem in these pupils are raised, at least temporarily, by separate instruction, academic performance however drops; combined instruction, on the other hand, leads to improved academic performance, while levels of self-esteem drop. Apparently, the positive self-image of less-able pupils who receive separate instruction does not bring about the potential enhancement of academic performance one might expect from high-ability pupils receiving separate instruction. To resolve the dilemma, it is proposed that individual progress in learning be accentuated, and that comparisons with others be dispensed with. This fosters a self-image that can in equal measure be realistic and optimistic.


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