Selective surface flow mechanism

Selective surface flow is, as Knudsen diffusion, associated with transport through microporous membranes, usually inorganic materials. The mechanism of surface diffusion is disputed and several different approaches have been proposed in the literature. 

Figure 22.7 Descriptions of nanoporous carbon membranes (a) mechanism of transport through the molecular sieve carbon (MSC) membrane, (b) mechanism of transport through the selective surface flow (SSF) membrane, (c) separation performance of H2S—H2 mixtures by the SSF membrane, (d) schematic drawing of a two-stage SSF membrane operation for Fl2S—FI2/CH4 separation.

The easily condensable CO2 molecule will follow a selective surface flow (SSF) mechanism and seriously hinder CH4 to permeate hence, high selectivities are obtained. 

Integration of a H2 PSA process with an adsorbent membrane can meet this goal [23, 24]. A nano-porous carbon adsorbent membrane called Selective Surface Flow (SSF) membrane which selectively permeates CO2, CO and CH4 from their mixtures with H2 by an adsorption- surface diffusion-desorption transport mechanism may be employed for this purpose. The SSF membrane can produce an enriched H2 gas stream from a H2 PSA waste gas, which can then be recycled as feed to the PSA process for increasing the over-all H2 recovery. The membrane is prepared by controlled carbonization of poly-vinyledene chloride supported on a macro-porous alumina tube. The membrane pore diameters are between 6 -7 A, and its thickness is - 1-2 pm [25]. 

Rao and Sircar [5-7] introduced nanoporous supported carbon membranes which were prepared by pyrolysis of PVDC layer coated on a macroporous graphite disk support. The diameter of the macropores of the dried polymer film was reduced to the order of nanometer as a result of a heat treatment at 1,000°C for 3 h. These membranes with mesopores could be used to separate hydrogen-hydrocarbon mixtures by the surface diffusion mechanism, in which gas molecules were selectively adsorbed on the pore wall. This transport mechanism is different from the molecular sieving mechanism. Therefore, these membranes were named as selective sitrface flow (SSF ) membranes. It consists of a thin (2-5 pm) layer of nanoporous carbon (effective pore diameter in the range of 5-6 A) supported on a mesoporous inert support such as graphite or alumina (effective pore diameter in the range of 0.3-1.0 pm). The procedures for making the selective surface flow membranes were described in [5, 7]. In particular, the requirements to produce a surface diffusion membrane were shown clearly in [7]. 

Porous membranes are characterized by high permeability, but low selectivity. The transport mechanisms in porous membranes can be viscous flow, Knudsen diffusion, surface diffusion, capillary condensation, and/ or molecular sieving, depending on the membrane pore size and its surface characteristics. The performance of porous MRs is very much dependent on the membrane structures. Close adherence to a rigid protocol is necessary to obtain membranes of consistent quality. 

We have summarized below recent results concerning spectroscopic / flow reactor investigations of hydrocarbons partial and total oxidation on different transition metal oxide catalysts. The aim of this study is to have more information on the mechanisms of the catalytic activity of transition metal oxides, to better establish selective and total oxidation ways at the catalyst surface, and to search for partial oxidation products from light alkane conversion. 

The combined use of the modem tools of surface science should allow one to understand many fundamental questions in catalysis, at least for metals. These tools afford the experimentalist with an abundance of information on surface structure, surface composition, surface electronic structure, reaction mechanism, and reaction rate parameters for elementary steps. In combination they yield direct information on the effects of surface structure and composition on heterogeneous reactivity or, more accurately, surface reactivity. Consequently, the origin of well-known effects in catalysis such as structure sensitivity, selective poisoning, ligand and ensemble effects in alloy catalysis, catalytic promotion, chemical specificity, volcano effects, to name just a few, should be subject to study via surface science. In addition, mechanistic and kinetic studies can yield information helpful in unraveling results obtained in flow reactors under greatly different operating conditions. 

ISEs are well suited for flow measurements because the instrumentation and signal handling are simple, the measurement is almost independent of the liquid flow-rate, the linear dynamic range is broad, the temperature dependence is not very pronounced and the measurement is selective (the selectivity is, however, a drawback in applications to chromatography). The experimental conditions are readily adjusted and often only consist of ionic strength and pH maintenance. ISEs with solid membranes usually exhibit better performance than liquid membrane electrodes and gas probes, because their response is faster and they are mechanically stronger. The most difficult problem is passivation of the electrodes in some media, for example, biological fluids or surface and waste waters. 

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