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.

替代燃料二甲醚的燃烧特性及其污染物甲醛的生成消耗机理研究

化石燃料的不可再生性决定了其不能长久为全球经济和科技的发展提供能源动力，从可持续发展和能源战略的角度考虑，能够替代石油及其衍生品的清洁替代燃料研究已经成为提高能源供应安全、改善环境污染问题、应对气候变化的重要措施，对替代燃料的研究和应用已经成为各方关注和开发的热点。 二甲醚(DME、CH3OCH3)是一种最简单的醚类，它不含C-C健，可以由天然气、煤、生物质燃料等大量制备，而且具有较高的辛烷值(55-60)，较低的碳氢化合物、CO排放，没有PM排放，因而被认为是一种非常有发展前景的发动机替代燃料，已经受到了广泛的关注。但是，在发动机燃用DME的实验研究表明，在其排气中有非常规污染物甲醛(HCHO)、乙醛(CH3CHO)，甲酸甲酯(HCOOCH3)等排放，这些有机污染物会对环境和人类健康产生严重的危害，在环保要求日益严格的趋势下，这就制约了二甲醚的规模化应用。因此，对二甲醚燃烧性能、氧化中间产物甲醛等的产生和排放机理、相关污染物抑制技术需要进行着重研究，这对二甲醚燃料规模化应用、相关二甲醚燃烧器设计、燃烧性能的优化以及污染物控制技术的研究等都有着重要的理论指导意义和参考价值。 为了充分理解二甲醚燃料的燃烧特性、非常规污染物甲醛的产生和消耗机理，本文以实验和二甲醚化学反应动力学机理为指导，对二甲醚预混燃烧的燃烧特性、相关污染物和甲醛产生和消耗的机理做了详细的研究；并针对二甲醚燃料的不同应用背景，对二甲醚燃料低温下的氧化和甲醛生成特性、DME与LPG掺混燃烧特性和甲醛生成消耗机理进行了深入的研究，具体工作有： 研究了二甲醚预混燃烧特性、火焰中甲醛等污染物的产生特性，建立了火焰中甲醛取样、测量的方法和实验平台。并对当量比和燃料流量对二甲醚预混燃烧的燃烧特性、甲醛生成特性影响进行了考察，实验结果表明二甲醚是一种优良的替代燃料，在二甲醚火焰中甲醛是其重要的中间产物，甲醛浓度分布与当量比和预混气流速密切相关。当量比一定时，随着预混气流速的增加，火焰中甲醛产生的范围变窄，且甲醛浓度峰值逐渐移向燃烧器出口，而甲醛产生的浓度峰值数值上相差不大，甲醛在形成峰值后被快速消耗，其浓度在0.1mm内下降到几乎为零；在二甲醚流量一定时，随着当量比的增加，火焰中产生了更多的甲醛，火焰中甲醛分布的范围也变宽，而且当量比越大，甲醛的消耗也变缓，在当量比为0.8时，甲醛浓度从峰值到被消耗距离变为2mm，远大于当量比0.6和0.7下0.1mm的消耗距离。 对二甲醚预混燃烧进行数值研究和化学动力反应机理分析后发现，在二甲醚燃烧中，二甲醚的氧化反应途径主要是通过脱氢生成CH3OCH2和在高温下的直接裂解反应而进行，其中脱氢反应是低温下二甲醚消耗的主要途径，而在高温反应阶段(T>1000K)，DME的直接裂解和燃料的脱氢反应共同起主导作用；非常规污染物甲醛通过DME脱氢产物CH3OCH2的裂解和外部氧化而生成，在高温时通过DME直接裂解后被氧化产生；甲醛的消耗反应则是通过与H、O、OH和CH3基的氧化反应而完成，其中与O、OH基的反应在燃烧中起主要作用。因此二甲醚燃烧中甲醛的抑制关键在燃烧中甲醛的消耗阶段，采取有效的技术措施，如优化燃烧器结构提高二甲醚燃烧室内的温度、在燃烧区保证充足的氧气供应等措施，加快甲醛的消耗速度以促进其被完全氧化，可以实现二甲醚燃烧中甲醛的零排放。 针对柴油发动机燃用DME燃料时，燃料在燃烧室停留时间过短，造成部分未燃二甲醚随尾气排放，对DME在低温下(<800K)的氧化特性和甲醛生成特性进行了实验研究。结果表明，二甲醚在200℃左右就开始发生氧化反应，在200~400℃温度范围内被氧化而生成大量中间产物甲醛，且在此温度范围内甲醛不易被氧化分解，而发动机尾气温度（一般在200~600℃之间）处于甲醛最易生成的范围，因此未燃二甲醚在尾气中发生低温氧化反应生成的甲醛，是发动机燃用DME而排放高浓度甲醛的重要来源。研究结论为柴油发动机燃用DME抑制非常规污染物甲醛的排放提供了新的参考。 DME作为替代燃料，部分替代及与其他石化系燃料掺混燃烧是目前的重要应用方向，对DME与LPG掺混燃烧特性和甲醛生成特性进行了实验研究，结果表明，在DME与LPG掺混燃烧中，固定当量比和燃料质量流量的条件下，两种燃料存在一个最佳掺混比，在此掺混比例下，混合燃料着火提前，燃料燃烧性能最佳；DME与LPG混合燃料中，二甲醚是燃烧中甲醛产生的主要来源，控制DME的完全氧化和燃烧是抑制DME与LPG掺混燃烧排放甲醛的主要途径，这为更好地应用DME与LPG混合燃料提供了参考。 能否清洁高效燃烧是决定替代燃料DME应用规模和途径中的关键任务，本文对DME燃烧特性、非常规污染物甲醛的生成排放特性、低温下DME的氧化特性、DME与LPG掺混燃烧特性的研究，从不用的应用方向和领域对DME清洁高效燃烧进行了探讨和研究，研究成果可以为清洁高效利用二甲醚、抑制甲醛排放，以及开发相关燃烧技术、燃烧器提供实验依据和理论指导。本文在DME燃烧特性和非常规污染物甲醛的产生与排放方面取得了具有创新性的研究结果。

Partial oxidation reforming of biomass fuel gas over nickel-based monolithic catalyst with naphthalene as model compound

With naphthalene as biomass tar model compound, partial oxidation reforming (with addition of O-2) and dry reforming of biomass fuel gas were investigated over nickel-based monoliths at the same conditions. The results showed that both processes had excellent performance in upgrading biomass raw fuel gas. Above 99% of naphthalene was converted into synthesis gases (H-2+CO). About 2.8 wt% of coke deposition was detected on the catalyst surface for dry reforming process at 750 degrees C during 108 h lifetime test. However, no Coke deposition was detected for partial oxidation reforming process, which indicated that addition of O-2 can effectively prohibit the coke formation. O-2 Can also increase the CH4 conversion and H-2/CO ratio of the producer gas. The average conversion of CH4 in dry and partial oxidation reforming process was 92% and 95%, respectively. The average H-2/CO ratio increased from 0.95 to 1.1 with the addition of O-2, which was suitable to be used as synthesis gas for dimethyl ether (DME) synthesis.

Bio-syngas production from biomass catalytic gasification

A promising application for biomass is liquid fuel synthesis, such as methanol or dimethyl ether (DME). Previous studies have studied syngas production from biomass-derived char, oil and gas. This study intends to explore the technology of syngas production from direct biomass gasification, which may be more economically viable. The ratio of H-2/CO is an important factor that affects the performance of this process. In this study, the characteristics of biomass gasification gas, such as H-2/CO and tar yield, as well as its potential for liquid fuel synthesis is explored. A fluidized bed gasifier and a downstream fixed bed are employed as the reactors. Two kinds of catalysts: dolomite and nickel based catalyst are applied, and they are used in the fluidized bed and fixed bed, respectively. The gasifying agent used is an air-steam mixture. The main variables studied are temperature and weight hourly space velocity in the fixed bed reactor. Over the ranges of operating conditions examined, the maximum H-2 content reaches 52.47 vol%, while the ratio of H-2/CO varies between 1.87 and 4.45. The results indicate that an appropriate temperature (750 degrees C for the current study) and more catalyst are favorable for getting a higher H-2/CO ratio. Using a simple first order kinetic model for the overall tar removal reaction, the apparent activation energies and pre-exponential factors are obtained for nickel based catalysts. The results indicate that biomass gasification gas has great potential for liquid fuel synthesis after further processing.

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.

STUDY OF BIMETALLIC COMPLEXES OF RARE-EARTH LITHIUM - SYNTHESIS AND CRYSTAL-STRUCTURE OF THE (LACL)DME(MU-2-CL)5(MU-3-CL) (LA.DME)LI(THF)2

The reaction between LaCl_3 and LiCl in THF at room temperature, with hexane as precipitant and glycol dimethyl ether as complexing agent, has been studied. A complex with the composition of (LaCl)DME(μ_2-Cl)_5(μ_3-Cl)(La·DME)Li(THF)_2 has been synthesized, its structure was studied by single crystal X-ray diffraction technique. The diffraction intensities were collected at about —100℃. The complex belongs to the triclinic space group P1 with α=11.123(3), 6=16.564(5), c=8.653(3)A, α=95.16(3), β=...

The effect of additives on Cu/HZSM-5 catalyst for DME synthesis

The addition of ZnO or ZrO2 into CuO/HZSM-5 was investigated for DME synthesis from syngas by using the reactive frontal chromatography method, TPR and in situ TPR. These promoters enhanced the catalytic activity of Cu/HZSM-5 and promotion with ZnO and ZrO2 produced a maximum activity, which could be explained by the improvement of the dispersion of Cu and the promotion of CuO reduction. The Cu+ species existing during the reaction have been detected, based on which a Cu-0 <-> Cu+1 redox cycle model was put forward.

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.

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).