A review is presented for various gas tranport mechanisms through microporous membranes of both polymeric and inorganic materials. Different transport modes manifest depending on the pore size and the flow regime, which is a function of pressure, temperature, and the inateraction between gas molecules and the pore walls. For microporous membranes whose pores are small and the intenal surface area huge, the surface diffusion becomes a significant factor. If the pores become even smaller, them the transport mechanism will be more of an activated diffusion type. When conditions are right capillary condensation will take place to create an enormous capillary pressure gradient, which will greatly enhance the permeation flux. At the same time the capillary condensate of the heavier component may block the membrane pores denying the passage of the lighter gas molecules. All of these phenomena will influence the separation of mixtures.

Two membrane-related research projects are now being developed in Japan and their main target is to develop new inorganic membranes. The first project is the R & D of membranes for carbon dioxide recovery at high temperature, conducted by the Japan Fine Ceramics Center (JFCC) and Japan Fine Ceramics Association (JFCA) under the supervision by the New Energy and Industrial Technologu Development Organization (NEDO). The second one is the R & D of membranes for petroleum refinery and chemical processes, conducted by the Japan High Polymer Center (JHPC) under the supervision by the Petroleum Energy Center (PEC). Cooperating with these projects researchers in many universities and research institutes have been publishing many interesting data of inorganic membranes manyfactured by various methods. Many such results are summarized and reported.

Gas separation science and technology is among the most rapidly growing areas involving membrane-based processes. Nitrogen enrichment of air, hydrogen recovery from a broad array of stream types, and removal of acid gases from natural gases are typical of the applications in this field. Great progress has been made in the discovery of guidelines optimization of polymer structures with simultaneously high permeabilities and selectivities for these important gas pairs. The development of thin-skinned asymmetric hollow fibers have also provided structures with extremely high permeation fluxes. Especially in the case of O$_{2}$/N$_{2}$ separations, the rate of improvements in new polymeric materials for gas separations appears to be slowing to a halt. Evidence will be presented, however, that the practical tradeoff between membrane permeability and selectivity has not been reached.

고분자막에 의한 기체분리는 심냉분리법, 흡수법, 흡착법등에 비하여 에너지가 절약되며 장치가 간결하고 운전비용이 낮은 이점 때문에 여러가지 기체혼합물에 대하여 여러가지 목적으로 응용되기에 이르렀다. O$_{2}$/N$_{2}$ 분리막으로 요구되는 기본특성은 1) 높은 O$_{2}$ 투과성 2) 높은 O$_{2}$ 선택성 3) 막 형성에 충분한 기계적 강도 4) 열, 화학적으로 안정성이 있어야 한다. 그런데 투과계수 P$_{O_(2)}$와 투과선택도 P$_{O_(2)}$/P$_{N_(2)}$ 관계 Fig.2 에서 보는 바와 샅이 대체로 투과선택성은 상반관계에 있어서 polyimide는 높은 선택성을 나타내고 기계적 강도가 좋고 높은 열에 대하여 안정하기 때문에 일단 막재료로 양호한 조건을 갖추고 있으나 투과계수가 크지 않아 선택도를 크게 감소시키지 않으면서 투과계수를 향성시키려는 노력이 경주되고 있다. 따라서 polyimide의 화학구조와 투과계수, 투과선택도의 관계를 고찰하는 것은 대단히 중요하다. 특히 최근에는 polyimide의 화학구조를 계통적으로 변화 시켜가면서 구조와 투과특성을 고찰한 연구가 많으며, 이러한 연구를 총망라하여 화학구조와 투과특성을 고찰한 훌륭한 총설들이 발표되어왔다. Fig.3에는 지금까지 연구된 중요한 polyimide를 형성하는 dianhydride와 diamine의 구조식을 표시하였으며 이들 구조의 변화에 의하여 기체투과계수와 투과선택도가 어떤 영향을 받는지 고찰하고자 한다.

Modified polycrylonitrile(PAN) membranes were prepared by emulsion or emulsifier-free emulsion polymerization technique. Separation capacity was determined at several operating temperatures(25, 40, 55 and 70 $^{\circ}$C) to dehydrate 56wt% pyridine aqueous solution through modified PAN membranes having different functional groups. All these PAN-based membranes were selective toward water to different degrees depending on the nature of functional groups present in the membranes. Pervaporation characteristics of PAN-based membranes are so different and classified into three categories depending on the type of the functional groups in PAN copolymers. Among PAN-based membranes, the in-situ complex membranes show the best separation capacity over the operating temperatures.

A simple mathematical model for gacilitated mass transport with a fixed site carrier membrane was derived by assuming an instantaneous, microscopic concentration (activity) fluctuation, The concentration fluctuation, developed due to reversible chemical reaction between carrier and solute, could acuse the higher chemical potential gradient and the facilitated transport. For mathematical formulation, an analogy was employed between the mass transfer for the facilitated transport with fixed site carrier membrane and the electron transfer in a parallel resistor-capacitor (RC) circuit. For the single RC model, it was assumed that a single capacitor represented the total carrier and a solute could not inter-diffuse between matrix and carrier, allowing only two diffusional pathways, This assumption was relaxed by adopting a serial combination of the parallel RC circuit. Here, a solute diffuses in two elements (matrix or carrier) can exchange its pathway, exhibiting four diffusional pathways. The current models were examined against experimental data and the agreement was exceptional.

The asymmetric hollow fiber membranes were prepared by the wet spining of polyetherimide dope solution and the effect of hollow fiber structures on the permeation characteristics of carbon dioxide and nitrogen gases through these membrane were investigated. As the concentration of the $\gamma$-butyrolactone (GBL) in dope solution, acting as a swelling agent was increased, the structure of hollow fiber was changed from the finger to sponge type. The permeabilities of gases (CO$_{2}$, N$_{2}$) through these membrane were measured over the wide range of pressure under different temperature. The effect of water vapor on the permeabilities of gases was also investigated. The measured permeabilities showed the different characteristics depending on the structure of membranes. It was found that the flow through the pores were dominant over the polymers matrix. Blocking effect by water vapor in the pores of skin layer greatly improved the ideal separation factor of carbon dioxide/nitrogen.