Adsorption of dimethyl ether (DME) on zeolite molecular sieves

In recent years there has been growing interest in the use of dimethyl ether (DME) as an alternative fuel. In this study, the adsorption of DME on molecular sieves 4Å (Mol4A) and 5Å (Mol5A) has been experimentally investigated using the volumetric adsorption method. Data on the adsorption isotherms, heats of adsorption, and adsorption kinetic have been obtained and used to draw conclusions and compare the performance of the two adsorbents. Within the conditions considered, the adsorption capacity of Mol5A was found to be around eight times higher than the capacity of Mol4A. Low temperature adsorption and thermal pre-treatment of the adsorbents in vacuum were observed to be favourable for increased adsorption capacity. The adsorption isotherms for both adsorbent were fitted to the Freundlich model and the corresponding model parameters are proposed. The adsorption kinetic analysis suggest that the DME adsorption on Mol5A is controlled by intracrystalline diffusion resistance, while on Mol4A it is mainly controlled by surface layering resistance with the diffusion only taking place at the start of adsorption and for a very limited short time. The heats of adsorption were calculated by a calorimetric method based on direct temperature measurements inside the adsorption cell. Isosteric heats, calculated by the thermodynamic approach (Clasius-Clapeyron equation), have consistently shown lower values. The maximum heat of adsorption was found to be 25.9kJmol-1 and 20.1kJmol-1 on Mol4A and Mol5A, respectively; thus indicating a physisorption type of interactions. © 2014 Elsevier B.V.

Computationsl modelling of dimethyl ether separation and steam reforming in fluidized bed reactors

This study presents a computational fluid dynamic (CFD) study of Dimethyl Ether (DME) gas adsorptive separation and steam reforming (DME-SR) in a large scale Circulating Fluidized Bed (CFB) reactor. The CFD model is based on Eulerian-Eulerian dispersed flow and solved using commercial software (ANSYS FLUENT). Hydrogen is currently receiving increasing interest as an alternative source of clean energy and has high potential applications, including the transportation sector and power generation. Computational fluid dynamic (CFD) modelling has attracted considerable recognition in the engineering sector consequently leading to using it as a tool for process design and optimisation in many industrial processes. In most cases, these processes are difficult or expensive to conduct in lab scale experiments. The CFD provides a cost effective methodology to gain detailed information up to the microscopic level. The main objectives in this project are to: (i) develop a predictive model using ANSYS FLUENT (CFD) commercial code to simulate the flow hydrodynamics, mass transfer, reactions and heat transfer in a large scale dual fluidized bed system for combined gas separation and steam reforming processes (ii) implement a suitable adsorption models in the CFD code, through a user defined function, to predict selective separation of a gas from a mixture (iii) develop a model for dimethyl ether steam reforming (DME-SR) to predict hydrogen production (iv) carry out detailed parametric analysis in order to establish ideal operating conditions for future industrial application. The project has originated from a real industrial case problem in collaboration with the industrial partner Dow Corning (UK) and jointly funded by the Engineering and Physical Research Council (UK) and Dow Corning. The research examined gas separation by adsorption in a bubbling bed, as part of a dual fluidized bed system. The adsorption process was simulated based on the kinetics derived from the experimental data produced as part of a separate PhD project completed under the same fund. The kinetic model was incorporated in FLUENT CFD tool as a pseudo-first order rate equation; some of the parameters for the pseudo-first order kinetics were obtained using MATLAB. The modelling of the DME adsorption in the designed bubbling bed was performed for the first time in this project and highlights the novelty in the investigations. The simulation results were analysed to provide understanding of the flow hydrodynamic, reactor design and optimum operating condition for efficient separation. Bubbling bed validation by estimation of bed expansion and the solid and gas distribution from simulation agreed well with trends seen in the literatures. Parametric analysis on the adsorption process demonstrated that increasing fluidizing velocity reduced adsorption of DME. This is as a result of reduction in the gas residence time which appears to have much effect compared to the solid residence time. The removal efficiency of DME from the bed was found to be more than 88%. Simulation of the DME-SR in FLUENT CFD was conducted using selected kinetics from literature and implemented in the model using an in-house developed user defined function. The validation of the kinetics was achieved by simulating a case to replicate an experimental study of a laboratory scale bubbling bed by Vicente et al [1]. Good agreement was achieved for the validation of the models, which was then applied in the DME-SR in the large scale riser section of the dual fluidized bed system. This is the first study to use the selected DME-SR kinetics in a circulating fluidized bed (CFB) system and for the geometry size proposed for the project. As a result, the simulation produced the first detailed data on the spatial variation and final gas product in such an industrial scale fluidized bed system. The simulation results provided insight in the flow hydrodynamic, reactor design and optimum operating condition. The solid and gas distribution in the CFB was observed to show good agreement with literatures. The parametric analysis showed that the increase in temperature and steam to DME molar ratio increased the production of hydrogen due to the increased DME conversions, whereas the increase in the space velocity has been found to have an adverse effect. Increasing temperature between 200 oC to 350 oC increased DME conversion from 47% to 99% while hydrogen yield increased substantially from 11% to 100%. The CO2 selectivity decreased from 100% to 91% due to the water gas shift reaction favouring CO at higher temperatures. The higher conversions observed as the temperature increased was reflected on the quantity of unreacted DME and methanol concentrations in the product gas, where both decreased to very low values of 0.27 mol% and 0.46 mol% respectively at 350 °C. Increasing the steam to DME molar ratio from 4 to 7.68 increased the DME conversion from 69% to 87%, while the hydrogen yield increased from 40% to 59%. The CO2 selectivity decreased from 100% to 97%. The decrease in the space velocity from 37104 ml/g/h to 15394 ml/g/h increased the DME conversion from 87% to 100% while increasing the hydrogen yield from 59% to 87%. The parametric analysis suggests an operating condition for maximum hydrogen yield is in the region of 300 oC temperatures and Steam/DME molar ratio of 5. The analysis of the industrial sponsor’s case for the given flow and composition of the gas to be treated suggests that 88% of DME can be adsorbed from the bubbling and consequently producing 224.4t/y of hydrogen in the riser section of the dual fluidized bed system. The process also produces 1458.4t/y of CO2 and 127.9t/y of CO as part of the product gas. The developed models and parametric analysis carried out in this study provided essential guideline for future design of DME-SR at industrial level and in particular this work has been of tremendous importance for the industrial collaborator in order to draw conclusions and plan for future potential implementation of the process at an industrial scale.

A computational model of hydrogen production by steam reforming of dimethyl ether in a large scale CFB reactor. Part II:parametric analysis

This study presents a computational parametric analysis of DME steam reforming in a large scale Circulating Fluidized Bed (CFB) reactor. The Computational Fluid Dynamic (CFD) model used, which is based on Eulerian-Eulerian dispersed flow, has been developed and validated in Part I of this study [1]. The effect of the reactor inlet configuration, gas residence time, inlet temperature and steam to DME ratio on the overall reactor performance and products have all been investigated. The results have shown that the use of double sided solid feeding system remarkable improvement in the flow uniformity, but with limited effect on the reactions and products. The temperature has been found to play a dominant role in increasing the DME conversion and the hydrogen yield. According to the parametric analysis, it is recommended to run the CFB reactor at around 300 °C inlet temperature, 5.5 steam to DME molar ratio, 4 s gas residence time and 37,104 ml gcat -1 h-1 space velocity. At these conditions, the DME conversion and hydrogen molar concentration in the product gas were both found to be around 80%.

Desidratação/oxidação seletiva de metanol recorrendo a catalisadores heterogéneos para a obtenção de biocombustíveis (DME e DMM)

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Química e Biológica

(Diethyleneglycol dimethyl ether)tris(1,1,1,5,5,5-hexafluoropentane-2,4-dionato)praseodymium(III)

The title compound, [Pr(C5HF6O2)(3)(C6H14O3)] or [Pr(hfpd)(3)(2g)], was prepared by the reaction of PrCl3.7H(2)O and hfpd-H (1,1,1,5,5,5-hexafiuoropentane-2,4-dione) in the presence of aqueous ammonia and recrystallization of the product from n-hexane in the presence of diglyme (2g). The metal atom is nine-coordinate, bonded to three bidentate beta-diketonato ligands and the polyether molecule.

Raman spectra of polymer electrolytes based on poly(ethylene glycol) dimethyl ether, lithium perchlorate, and the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate

Raman spectra of polymer electrolytes based on poly(ethylene glycol) dimethyl ether (PEGdME) with LiClO(4), PEGdME/LiClO(4), and the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate, PEGdME/[bmim]PF(6), are compared. Raman spectroscopy suggests stronger interactions in PEGdME/LiClO(4) than PEGdmE/[bmim]PF(6), thus corroborating previous results obtained by molecular dynamics simulations. Quantum Chemistry methods have been used to calculate vibrational frequencies and the equilibrium structure of segments of the polymer chain around the cation. A consistent picture has been obtained from Raman spectroscopy, density functional theory (DFT) calculations, and molecular dynamics simulations for these polymer electrolytes. (C) 2010 Elsevier B.V. All rights reserved.

Study of optical properties and molecular structure of plasma polymerized diethylene glycol dimethyl ether

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Wettability, optical properties and molecular structure of plasma polymerized diethylene glycol dimethyl ether

Modern industry has frequently employed ethylene glycol ethers as monomers in plasma polymerization process to produce different types of coatings. In this work we used a stainless steel plasma reactor to grow thin polymeric films from low pressure RF excited plasma of diethylene glycol dimethyl ether. Plasmas were generated at 5W RF power in the range of 16 Pa to 60 Pa. The molecular structure of plasma polymerized films and their optical properties were analyzed by Fourier Transform Infrared Spectroscopy (FTIR) and UltravioletVisible Spectroscopy, respectively. The IR spectra show C-H stretching at 3000-2900 cm(-1), C=O stretching at 1730-1650 cm(-1), C-H bending at 1440-1380 cm(-1), C-O and C-O-C stretching at 1200-1000 cm(-1). The refraction index was around 1.5 and the optical gap calculated from absorption coefficient presented value near 3.8 eV. Water contact angle of the films ranged from 40 degrees to 35 degrees with corresponding surface energy from 66 to 73x10(-7) J. Because of its favorable optical and hydrophilic characteristics these films can be used in ophthalmic industries as glass lenses coatings.

Study of RF-excited Diethylene Glycol Dimethyl Ether Plasmas by Mass Spectrometry

This paper deals with the study of the fragmentation process of diethylene glycol dimethyl ether (CH3O(CH2CH2O)(2)CH3) (diglyme here in) molecule in low pressure RF excited plasma discharges. The study was carried out using mass spectrometry. The results showed that for a fixed pressure, the increase of the RF power coupled to the plasma chamber from 1 to 35 W produced a plasma environment much more reactive which increases the population of the ionized species like CH3+ (15 amu), C2H4+ (28 amu), CH3O+ (31 amu), C2H4O+ (44 amu), CH3OCH2CH2+ (59 amu) and CH3OCH2CH2O+ (75 amu). This fact may be attributed to the increase of the electronic temperature that makes predominant the occurrence of inelastic processes that promotes molecular fragmentation. For a fixed value of RF power the increase of pressure from 50 mTorr to 100 mTorr produces the decreasing of the above mentioned chemical species due the lower electronic mean free path. These results suggest that if one wants to keep the monomer's functionality within the plasma deposited films resulting from such kind of discharges one must operate in low power conditions.

Raman and infrared spectra of dimethyl ether 13C-isotopologue (CH3O13CH3) from a CCSD(T) potential energy surface

So far, no experimental data of the infrared and Raman spectra of 13C isotopologue of dimethyl ether are available. With the aim of providing some clues of its low-lying vibrational bands and with the hope of contributing in a next spectral analysis, a number of vibrational transition frequencies below 300 cm−1 of the infrared spectrum and around 400 cm−1 of the Raman spectrum have been predicted and their assignments were proposed. Calculations were carried out through an ab initio three dimensional potential energy surface based on a previously reported one for the most abundant dimethyl ether isotopologue (M. Villa et al., J. Phys. Chem. A 115 (2011) 13573). The potential function was vibrationally corrected and computed with a highly correlated CCSD(T) method involving the COC bending angle and the two large amplitude CH3 internal rotation degrees of freedom. Also, the Hamiltonian parameters could represent a support for the spectral characterization of this species. Although the computed vibrational term values are expected to be very accurate, an empirical adjustment of the Hamiltonian has been performed with the purpose of anticipating some workable corrections to any possible divergence of the vibrational frequencies. Also, the symmetry breaking derived from the isotopic substitution of 13C in the dimethyl ether was taken into account when the symmetrization procedure was applied.

Methyl chloride purification for the silicone industry

This study experimentally investigated methyl chloride (MeCl) purification method using an inhouse designed and built volumetric adsorption/desorption rig. MeCl is an essential raw material in the manufacture of silicone however all technical grades of MeCl contain concentrations (0.2 - 1.0 % wt) of dimethyl ether (DME) which poison the process. The project industrial partner had previously exhausted numerous separation methods, which all have been deemed not suitable for various reasons. Therefore, adsorption/desorption separation was proposed in this study as a potential solution with less economic and environmental impact. Pure component adsorption/desorption was carried out for DME and MeCl on six different adsorbents namely: zeolite molecular sieves (types 4 Å and 5 Å); silica gels (35-70 mesh, amorphous precipitated, and 35-60 mesh) and granular activated carbon (type 8-12 mesh). Subsequent binary gas mixture adsorption in batch and continuous mode was carried out on both zeolites and all three silica gels following thermal pre-treatment in vacuum. The adsorbents were tested as received and after being subjected to different thermal and vacuum pre-treatment conditions. The various adsorption studies were carried out at low pressure and temperature ranges of 0.5 - 3.5 atm and 20 - 100 °C. All adsorbents were characterised using Brunauer Emmett Teller (BET), thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and energy dispersive x-ray analysis (EDXA) to investigate their physical and chemical properties. The well-known helium (He) expansion method was used to determine the empty manifold and adsorption cell (AC) regions and respective void volumes for the different adsorbents. The amounts adsorbed were determined using Ideal gas laws via the differential pressure method. The heat of adsorption for the various adsorbate-adsorbent (A-S) interactions was calculated using a new calorimetric method based on direct temperature measurements inside the AC. Further adsorption analysis included use of various empirical and kinetic models to determine and understand the behaviour of the respective interactions. The gas purification behaviour was investigated using gas chromatography and mass spectroscopy (GC-MC) analysis. Binary gas mixture samples were syringed from the manifold iii and AC outlet before and after adsorption/desorption analysis through manual sample injections into the GC-MS to detect and quantify the presence of DME and ultimately observe for methyl chloride purification. Convincing gas purification behaviour was confirmed using two different GC columns, thus giving more confidence on the measurement reliability. From the single pure component adsorption of DME and MeCl on the as received zeolite 4A subjected to 1 h vacuum pre-treatment, both gases exhibited pseudo second order adsorption kinetics with DME exhibiting a rate constant nearly double that of MeCl thus suggesting a faster rate of adsorption. From the adsorption isotherm classification both DME and MeCl exhibited Type II and I adsorption isotherm classifications, respectively. The strength of bonding was confirmed by the differential heat of adsorption measurement, which was found to be 23.30 and 10.21 kJ mol-1 for DME and MeCl, respectively. The former is believed to adsorb heterogeneously through hydrogen bonding whilst MeCl adsorbs homogenously via van der Waal’s (VDW) forces. Single pure component adsorption on as received zeolite 5A, silica gels (35-70, amorphous precipitated and 35-60) resulted in similar adsorption/desorption behaviour in similar quantities (mol kg-1). The adsorption isotherms for DME and MeCl on zeolite 5A, silica gels (35-70, amorphous precipitated and 35-60) and activated carbon 8-12 exhibited Type I classifications, respectively. Experiments on zeolite 5A indicated that DME adsorbed stronger, faster and with a slightly stronger strength of interaction than MeCl but in lesser quantities. On the silica gels adsorbents, DME exhibited a slightly greater adsorption capacity whilst adsorbing at a similar rate and strength of interaction compared to MeCl. On the activated carbon adsorbent, MeCl exhibited the greater adsorption capacity at a faster rate but with similar heats of adsorption. The effect of prolonged vacuum (15 h), thermal pre-treatment (150 °C) and extended equilibrium time (15 min) were investigated for the adsorption behaviour of DME and MeCl on both zeolites 4A and 5A, respectively. Compared to adsorption on as received adsorbents subjected to 1 h vacuum the adsorption capacities for DME and MeCl were found to increase by 1.95 % and 20.37 % on zeolite 4A and by 4.52 % and 6.69 % on zeolite 5A, respectively. In addition the empirical and kinetic models and differential heats of adsorption resulted in more definitive fitting curves and trends due to the true equilibrium position of the adsorbate with the adsorbent. Batch binary mixture adsorption on thermally and vacuum pre-treated zeolite 4A demonstrated purification behaviour of all adsorbents used for MeCl streams containing DME impurities, with a concentration as low as 0.66 vol. %. The GC-MS analysis showed no DME detection for the tested concentration mixtures at the AC outlet after 15 or 30 min, whereas MeCl was detectable in measurable amounts. Similar behaviour was also observed when carrying out adsorption in continuous mode. On the other hand, similar studies on the other adsorbents did not show such favourable MeCl purification behaviour. Overall this study investigated a wide range of adsorbents (zeolites, silica gels and activated carbon) and demonstrated for the first time potential to purify MeCl streams containing DME impurities using adsorption/desorption separation under different adsorbent pre-treatment and adsorption operating conditions. The study also revealed for the first time the adsorption isotherms, empirical and kinetic models and heats of adsorption for the respective adsorbentsurface (A-S) interactions. In conclusion, this study has shown strong evidence to propose zeolite 4A for adsorptive purification of MeCl. It is believed that with a technical grade MeCl stream competitive yet simultaneous co-adsorption of DME and MeCl occurs with evidence of molecular sieiving effects whereby the larger DME molecules are unable to penetrate through the adsorbent bed whereas the smaller MeCl molecules diffuse through resulting in a purified MeCl stream at the AC outlet. Ultimately, further studies are recommended for increased adsorption capacities by considering wider operating conditions, e.g. different adsorbent thermal and vacuum pre-treatment and adsorbing at temperatures closer to the boiling point of the gases and different conditions of pressure and temperature.

Hydrogen production by steam reforming of DME in a large scale CFB reactor. Part I:computational model and predictions

This study presents a computational fluid dynamic (CFD) study of Dimethyl Ether steam reforming (DME-SR) in a large scale Circulating Fluidized Bed (CFB) reactor. The CFD model is based on Eulerian-Eulerian dispersed flow and solved using commercial software (ANSYS FLUENT). The DME-SR reactions scheme and kinetics in the presence of a bifunctional catalyst of CuO/ZnO/Al2O3+ZSM-5 were incorporated in the model using in-house developed user-defined function. The model was validated by comparing the predictions with experimental data from the literature. The results revealed for the first time detailed CFB reactor hydrodynamics, gas residence time, temperature distribution and product gas composition at a selected operating condition of 300 °C and steam to DME mass ratio of 3 (molar ratio of 7.62). The spatial variation in the gas species concentrations suggests the existence of three distinct reaction zones but limited temperature variations. The DME conversion and hydrogen yield were found to be 87% and 59% respectively, resulting in a product gas consisting of 72 mol% hydrogen. In part II of this study, the model presented here will be used to optimize the reactor design and study the effect of operating conditions on the reactor performance and products.

Preliminary study of synthesis gas production from water electrolysis, using the ELECTROFUEL (R) concept

This paper describes preliminary work on the generation of synthesis gas from water electrolysis using graphite electrodes without the separation of the generated gases. This is an innovative process, that has no similar work been done earlier. Preliminary tests allowed to establish correlations between the applied current to the electrolyser and flow rate and composition of the generated syngas, as well as a characterisation of generated carbon nanoparticles. The obtained syngas can further be used to produce synthetic liquid fuels, for example, methane, methanol or DME (dimethyl ether) in a catalytic reactor, in further stages of a present ongoing project, using the ELECTROFUEL® concept. The main competitive advantage of this project lies in the built-in of an innovative technology product, from RE (renewable energy) power in remote locations, for example, islands, villages in mountains as an alternative for energy storage for mobility constraints.

Stereoselective syntheses of (+/-)-komaroviquinone and (+/-)-faveline methyl ether through intramolecular Heck reaction

An efficient, flexible, and stereoselective convergent route for constructing the trans-10-hydroxy1,1-dimethyloctahydrodibenzo[a,d]cyclohepten-7-ones (5a-c) was achieved via intramolecular Heck reaction. This strategy has been successfully implemented for the syntheses of (+/-)-komaroviquinone (3) through (+/-)-coulterone dimethyl ether (5c) and (+/-)-faveline methyl ether (1a).

CCSD(T) Study of CD3-O-CD3 and CH3-O-CD3 Far-Infrared Spectra

From a vibrationally corrected 3D potential energy surface determined with highly correlated ab initio calculations (CCSD(T)), the lowest vibrational energies of two dimethyl-ether isotopologues, 12CH3–16O–12CD3 (DME-d3) and 12CD3–16O–12CD3 (DME-d6), are computed variationally. The levels that can be populated at very low temperatures correspond to the COC-bending and the two methyl torsional modes. Molecular symmetry groups are used for the classification of levels and torsional splittings. DME-d6 belongs to the G36 group, as the most abundant isotopologue 12CH3–16O–12CH3 (DME-h6), while DME-d3 is a G18 species. Previous assignments of experimental Raman and far-infrared spectra are discussed from an effective Hamiltonian obtained after refining the ab initio parameters. Because a good agreement between calculated and experimental transition frequencies is reached, new assignments are proposed for various combination bands corresponding to the two deuterated isotopologues and for the 020 → 030 transition of DME-d6. Vibrationally corrected potential energy barriers, structural parameters, and anharmonic spectroscopic parameters are provided. For the 3N – 9 neglected vibrational modes, harmonic and anharmonic fundamental frequencies are obtained using second-order perturbation theory by means of CCSD and MP2 force fields. Fermi resonances between the COC-bending and the torsional modes modify DME-d3 intensities and the band positions of the torsional overtones.