Hydrogen dense membranes

Dense membranes are a special type of polymeric membranes. Jacobs et al. published on the use of polydimethylsiloxane (PDMS) dense membranes in the hydrogenation of dimethylitaconate and acetophenone using standard homogeneous catalysts (see Section 4.6.1)[48]. The membranes were homemade from a PDMS solution in hexane, which was cross-linked in a vacuum oven at 100°C. The membranes were able almost completely to retain unmodified Ru-BINAP dissolved in isopropanol. However, as mentioned earlier, these applications will strongly depend on the size, i.e. molecular weight, of the substrate to be converted in order to guarantee a sufficient difference in size of the product and the catalyst to be retained. 

Inorganic membranes can be categorized as shown in Table 2.1. The dense inorganic membranes consist of solid layers of metals (Pd, Ag, alloys) or (oxidic) solid electrolytes which allow diffusion of hydrogen (or oxygen). In the case of solid electrolytes transport of ions takes place. Another category of dense membranes consist of a porous support in which a liquid is... 

A second class of membranes are described as dense membranes. They may consist of thin plates of metals (Pd and its alloys, Ag and some alloys) or oxides (stabilized zirconia or bismuth oxides, cerates). These membranes are permeable to atomic (for metals) or ionic (for oxides) forms of hydrogen or oxygen and have been studied, especially, in conjunction with chemical... 

As explained in Chapter 5, the transport mechanism in dense crystalline materials is generally made up of incessant displacements of mobile atoms because of the so-called vacancy or interstitial mechanisms. In this sense, the solution-diffusion mechanism is the most commonly used physical model to describe gas transport through dense membranes. The solution-diffusion separation mechanism is based on both solubility and mobility of one species in an effective solid barrier [23-25], This mechanism can be described as follows first, a gas molecule is adsorbed, and in some cases dissociated, on the surface of one side of the membrane, it then dissolves in the membrane material, and thereafter diffuses through the membrane. Finally, in some cases it is associated and desorbs, and in other cases, it only desorbs on the other side of the membrane. For example, for hydrogen transport through a dense metal such as Pd, the H2 molecule has to split up after adsorption, and, thereafter, recombine after diffusing through the membrane on the other side (see Section 5.6.1). 

Transport in porous membranes occurs via diffusion of gaseous molecules within the porous framework this transport may involve different mechanisms (Section A9.3.2.4) which are more or less dependent on the nature of the gaseous molecules, and hence more or less efficient for the separation of a gas mixture. Porous membranes are therefore generally less permselective when compared to dense ones however, their permeability is higher (a conventional mesoporous y-Al2C>3 membrane has a permeability for hydrogen which is 10 to 100 times higher than a conventional Pd dense membrane. More detailed permeability data can be found in Ref. 9). 

In the case of dense membranes, where only hydrogen can permeate (permselectivity for H2 is infinite), the permeation rate is generally much lower than the reaction rate (especially when a fixed bed is added to the membrane). Experimental conditions and/or a reactor design which diminishes this gap will have positive effects on the yield. An increase of the sweep gas flow rate (increase of the driving force for H2 permeation) leads to an increase in conversion and, if low reactant flow rates are used (to limit the H2 production), conversions of up to 100% can be predicted [55]. These models of dense membrane reactors explain why large membrane surfaces are needed and why research is directed towards decreasing the thickness of Pd membranes (subsection 9.3.2.2.A.a). 

Chapter 6 Dense Membranes for Hydrogen Separation and Purification..147... 

As discussed earlier, many composite porous membranes have one or more intermediate layers to avoid substantial penetration of fme particles from the selective layer into the pores of the bulk support matrix for maintaining adequate membrane permeability and sometimes to enhance the adhesion between the membrane and the bulk support The same considerations should also apply when forming dense membranes on porous supports. This is particularly true for expensive dense membrane materials like palladium and its alloys. In these cases, organic polymeric materials are sometimes used and some of them like polyarilyde can withstand a temperature of up to 350X in air and possess a high hydrogen selectivity [Gryaznov, 1992]. 

Gas/vapor phase hydrogen-consuming reactions using dense membrane reacimrs... 

Gas/vapor phase hydrogen-generating reactions using dense membrane reactors... 

Similar to the case of dehydrogenation or other hydrogen-generating reactions, the use of a dense membrane reactor to remove oxygen from an oxygen-generating reaction such as decomposition of carbon dioxide displaces the reaction equilibrium and increases the conversion from 1.2% (limited by the equilibrium) to 22% [Nigara and Cales, 1986]. This has been confumed by Itoh et al. [1993]. 

Shown in Table 8.6 arc some literature data on the use of dense membrane reactors for liquid- or multi-phase catalytic reactions. Compared to gas/vapor phase application studies, these investigations are relatively few in number. Most of them involve hydrogenation reactions of various chemicals such as acetylenic or ethylenic alcohols, acetone, butynediol, cyclohexane, dehydrolinalool, phenylacetylene and quinone. As expected, the majority of the materials adopted as membrane reactors are palladium alloy membranes. High selectivities or yields are observed in many cases. A higher conversion than that in a conventional reactor is found in a few cases. 

There has been a large volume of data showing the benefit of having thin dense membranes (mostly Pd-based) on the hydrogen permeation rate and therefore the reaction conversion. An example is catalytic dehydrogenation of propane using a ZSM-5 based zeolite as the catalyst and a Pd-based membrane. Clayson et al. [1987] selected a membrane thickness of 100 m and achieved a yield of aromatics of 38% compared to approximately 80% when a 8.6 pm thick membrane is used [Uemiya et al., 1990]. 

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