Abstak desrtasi Gas Adsorption and Permeation in MFI Zeolites and Membranes AUTHOR: Sang Kompiang Wirawan; Chalmers

Tekniska Hgskola.; Chalmers University Of Technology.; [2009] KEYWORDS: TEKNIKVETENSKAP; TECHNOLOGY; MFI zeolites; adsorption; FTIR spectra; TPD; composite membranes; WGS membrane reactor; ABSTRACT: The single and multi component gas adsorption behavior on silicalite-1 and cation exchanged MZSM-5 zeolites (M = H, Na, and Ba) were investigated by a step change response method. Temperature programmed desorption (TPD) and in-situ fourier transform infrared (FTIR) spectroscopy were also performed to study the type of adsorbed species and their thermal stabilities. It was found that CO2 was adsorbed on silicalite and HZSM-5 as one type of adsorbed species, and on NaZSM-5 and BaZSM-5 zeolites as at least two types of adsorbed species over the temperature range studied. The CO2 adsorption behavior for silicalite and HZSM-5 was adequately described by a single site Langmuir adsorption model but for NaZSM-5 and BaZSM-5 a dual site Langmuir model was required. FTIR-spectra revealed that CO2 was adsorbed on MZSM-5 and silicalite in several ways and formed carbonate bands, which seemed to be caused by different adsorption sites. The multi-component adsorption behavior is adequately predicted by an extended Langmuir model, but failed to describe the CO2 adsorption on BaZSM-5 for a H2/CO2 gas mixture. Single and binary H2/CO2 gas permeation was studied through a silicalite-1 composite membrane over a temperature range 25 to 300oC. In general, single component fluxes decreased with increasing temperature whereas binary component fluxes showed a maximum followed by a continuous decrease. A complete mass transport model including surface diffusion and gas translational diffusion in zeolite crystals, Knudsen diffusion in defects, as well as viscous flow and Knudsen diffusion in the support material was developed to simulate the single and binary gas permeation measurements. The modeling results showed that surface diffusion was the dominant mass transport mechanism, and also the transport resistance of the support material was not negligible. The feasibility of a water gas shift (WGS) membrane reactor was evaluated in a modeling study. A Silicalite-1 membrane was considered to be integrated into a WGS reactor operating under conditions favorable for selective CO2 permeation in the membrane. The modeling study showed that both the WGS reaction rate and the CO2/H2 permeation played an important role on the overall reactor performance. Lower outlet CO concentration then the equivalent equilibrium composition could be achieved, but not levels required for a PEM fuel cell with an acceptable H2 recovery. This is due to the fact that sufficiently high CO2/H2 selective permeation cannot be achieved with a silicalite-1 membrane.

Ethanol Production from Lignocellulosic Materials: Potential of Continuous Cultivation, Immobilisation, and Zygomycetous Fungi AUTHOR: Ria Millati; Chalmers Tekniska Hgskola.; Chalmers University Of Technology.; [2005] KEYWORDS: TEKNIKVETENSKAP; TECHNOLOGY; ethanol; dilute-acid hydrolysate; continuous cultivation; detoxification; immobilisation; overliming; Rhizopus; Mucor; Rhizomucor; M indicus; S cerevisiae; glucose; mannose; galactose; xylose; arabinose; ABSTRACT: This thesis deals with the production of bio-ethanol, a sustainable alternative to fossil fuels, from dilute-acid lignocellulosic hydrolysate in a continuous immobilised cell system and fermentation of the hydrolysate by a zygomycete organism, M. indicus. An immobilised cell system was applied in order to increase the ethanol productivity in continuous cultivation. While the traditional continuous cultivation on the hydrolysate could only be carried out with a dilution rate of less than 0.2 h-1, the immobilised cells allowed up to 0.6 h-1. Immobilised cells in continuous cultivation could also accomplish in situ detoxification against the effects of the inhibitors. Of known inhibitors, almost all furfural and 60% of HMF were converted. Yet continuous cultivation of severely inhibiting hydrolysate was not successful without detoxification. Detoxification with overliming was intended to remove the inhibitors. The effects of different variables in overliming were investigated for the severely inhibiting hydrolysates. The process involves increasing pH with Ca(OH)2 to 10, 11 or 12 at temperature 25C and 60C, and holding the alkali pH and the temperature at constant values for times up to 170 h. The most significant effect of overliming was a sharp decrease in the concentration of furfural and HMF, whereas the concentration of acetic acid remained unchanged and the decrease in the total phenolic compounds was less than 30%. The fermentability was improved at the expense of sugar loss to different degrees according to the conditions applied. In a study of alternative organisms from the class of zygomycetes for fermentation of dilute-acid lignocellulosic hydrolysate, three genera of Rhizopus, Mucor and Rhizomucor were tested. M. indicus showed promising characteristics as an ethanol producer. The degree of aeration was found to affect the broad range of sugar consumption and the ethanol yield. Under aerobic conditions, M. indicus could consume glucose, mannose, galactose, xylose, arabinose and sugars within the dilute-acid hydrolysate. Under anaerobic conditions, xylose was not consumed, while hexoses were comsumed and yielded up to 0.46 g/g ethanol. On the other hand, aeration allowed xylose utilisation by M. indicus, but its ethanol yield depended on the rate of aeration, with the highest yield of 0.18 g/g. Cultivation of the fungus in dilute-acid hydrolysate including hexoses and xylose resulted in ethanol yield of 0.44 g/g under anaerobic and oxygen-limited conditions. M. indicus produced metabolites similar to those of baker's yeast, S. cerevisiae, with ethanol as the main metabolite as well as glycerol and trace amounts of several carboxylic acids as the by-products.