Internal surface modification of zeolite MFI particles and membranes for gas separation
Kassaee, Mohamad Hadi
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Zeolites are a well-known class of crystalline oxide materials with tunable compositions and nanoporous structures, and have been used extensively in catalysis, adsorption, and ion exchange. The zeolite MFI is one of the well-studied zeolites because it has a pore size and structure suitable for separation or chemical conversion of many industrially important molecules. Modification of zeolite structures with organic groups offers a potential new way to change their properties of zeolites, beyond the manipulation of the zeolite framework structure and composition. The main goals of this thesis research are to study the organic-modification of the MFI pore structure, and to assess the effects of such modification on the adsorption and transport properties of zeolite MFI sorbents and membranes. In this work, the internal pore structure of MFI zeolite particles and membranes has been modified by direct covalent condensation or chemical complexation of different organic molecules with the silanol defect sites existing in the MFI structure. The organic molecules used for pore modification are 1-butanol, 1-hexanol, 3-amino-1-propanol, 1-propaneamine, 1,3-diaminopropane, 2-[(2-aminoethyl)amino]ethanol, and benzenemethanol. TGA/DSC and 13C/29Si NMR characterizations indicated that the functional groups were chemically bound to the zeolite framework, and that the loading was commensurate with the concentration of internal silanol defects. Gas adsorption isotherms of CO2, CH4, and N2 on the modified zeolite materials show a range of properties different from that of the bare MFI zeolite. The MFI/3-amino-1-propanol, MFI/2-[(2-aminoethyl)amino]ethanol, and MFI/benzenemethanol materials showed the largest differences from bare MFI. These properties were qualitatively explained by the known affinity of amino- and hydroxyl groups for CO2, and of the phenyl group for CH4. The combined influence of adsorption and diffusion changes due to modification can be studied by measuring permeation of different gases on modified MFI membranes. To study these effects, I synthesized MFI membranes with [h0h] out-of-plane orientation on α-alumina supports. The membranes were modified by the same procedures as used for MFI particles and with 1-butanol, 3-amino-1-propanol, 2-[(2-aminoethyl)amino]ethanol, and benzenemethanol. The existence of functional groups in the pores of the zeolite was confirmed by PA-FTIR measurements. Permeation measurements of H2, N2, CO2, CH4, and SF6, were performed at room temperature before and after modification. Permeation of n-butane, and i-butane were measured before and after modification with 1-butanol. For all of the studied gases, gas permeances decreased by 1-2 orders of magnitude compared to bare MFI membranes for modified membranes. This is a strong indication that the organic species in the MFI framework are interacting with or blocking the gas molecule transport through the MFI pores. A detailed fundamental study of the CO2 adsorption mechanism in modified zeolites is necessary to gain a better understating of the adsorption and permeation behavior of such materials. Towards this end, an in situ FTIR study was performe.For the organic molecules with only one functional group (1-butanol, benzenemethanol, and 1-propaneamine), physical adsorption was found - as intuitively expected - to be the only observed mode of attachment of CO2 to the modified zeolite material. Even in the case of MFI modified with 1,3-diaminopropane, only physical adsorption is seen. This is explained by the isolated nature of the amine groups in the material, due to which only a single amine group can interact with a CO2 molecule. On the other hand, chemisorbed CO2 species are clearly observed on bare MFI, and on MFI modified with 3-amino-1-propanol or 2-[(2-aminoethyl)amino]ethanol. Specifically, these are carbonate-like species that arise from the chemisorption of CO2 to the silanol group in bare MFI and the alcohol groups of the modifying molecule. The possibility of significant contributions from external surface silanol groups in adsorbing CO2 chemisorbed species was ruled out by a comparative examination of the FTIR spectra of 10 μm and 900 nm MFI particles modified with 2-[(2-aminoethyl)amino]ethanol.