Gas-Separation Applications

Gas separation processes with membranes have undergone a major evolution since the introduchon of the first membrane-based industrial hydrogen separation process about two decades ago. The development of high selectivity mixed-matrix membranes will further advance the technology of membrane gas separation processes within the next decade. 

ZeoHte/polymer mixed-matrix membranes have been studied for a number of gas separations such as separation of N2 from air [37, 73, 75, 81, 84, 85], H2 and CO2 removal from natural gas [51, 54, 69, 81, 86-88], CO2 removal from N2 [74], n-pentane/i-pentane separation ]89] and separation of H2 from CO2 [65]. But a majority of the mixed-matrix membranes that have been evaluated for gas separations are mixed-matrix dense films. 

Rubbery polymer, polydimethylsiloxane (PDMS), was used as the polymer matrix to prepare zeolite/PDMS mixed-matrix membranes [82, 89]. This type of mixed-matrix membrane, however, did not exhibit improved selectivity for n-pentane/i-pentane separation relative to the neat PDMS membrane. 

Organosilane coupling agents have been widely used to improve the adhesion at the zeolite/polymer interface of the mixed-matrix membranes ]62, 63, 65, 70]. 

The well-adhered interface resulted in defect-free mixed-matrix membranes with some improved performance for CO2/CH4 separation. 

---

In gas separation applications, polymeric hollow fibers (diameter X 100 fim) are used (e.g. PAN) with a dense skin. In the skin the micropores develop during pyrolyzation. This is also the case in the macroporous material but is not of great importance from gas permeability considerations. Depending on the pyrolysis temperature, the carbon membrane top layer (skin) may or may not be permeable for small molecules. Such a membrane system is activated by oxidation at temperatures of 400-450 C. The process parameters in this step determine the suitability of the asymmetric carbon membrane in a given application (Table 2.8). 

Pressure swing adsorption (PSA) processes are widely applied industrially for gas separations. Applications are numerous and include hydrogen and helium recovery and purification, air drying, the production of oxygen from air, and the separation of normal paraffins from isoparaffins. 

The types of hollow fiber membranes in production are illustrated in Figure 3.32. Fibers of 50- to 200-p.m diameter are usually called hollow fine fibers. Such fibers can withstand very high hydrostatic pressures applied from the outside, so they are used in reverse osmosis or high-pressure gas separation applications in which the applied pressure can be 1000 psig or more. The feed fluid is applied to the outside (shell side) of the fibers, and the permeate is removed down the fiber bore. When the fiber diameter is greater than 200-500 xm, the feed fluid is commonly applied to the inside bore of the fiber, and the permeate is removed from the outer shell. This technique is used for low-pressure gas separations and for applications such as hemodialysis or ultrafiltration. Fibers with a diameter greater than 500 xm are called capillary fibers. 

Another method of producing composite hollow fibers, described by Kusuki etal. at Ube [108] and Kopp et al. at Memtec [109], is to spin double-layered fibers with a double spinneret of the type shown in Figure 3.37. This system allows different spinning solutions to be used for the outer and inner surface of the fibers and gives more precise control of the final structure. Often, two different polymers are incorporated into the same fiber. The result is a hollow fiber composite membrane equivalent to the flat sheet membrane shown in Figure 3.26. A reason for the popularity of composite hollow fiber membranes is that different polymers can be used to form the mechanically strong support and the selective layer. This can reduce the amount of selective polymer required. The tailor-made polymers developed for gas separation applications can cost as much as... 

Figure 3.42 Exploded view and cross-section drawings of a spiral-wound module. Feed solution passes across the membrane surface. A portion passes through the membrane and enters the membrane envelope where it spirals inward to the central perforated collection pipe. One solution enters the module (the feed) and two solutions leave (the residue and the permeate). Spiral-wound modules are the most common module design for reverse osmosis and ultrafiltration as well as for high-pressure gas separation applications in the natural gas industry...

Two other major factors determining module selection are concentration polarization control and resistance to fouling. Concentration polarization control is a particularly important issue in liquid separations such as reverse osmosis and ultrafiltration. In gas separation applications, concentration polarization is more easily controlled but is still a problem with high-flux, highly selective membranes. Hollow fine fiber modules are notoriously prone to fouling and concentration polarization and can be used in reverse osmosis applications only when extensive, costly feed solution pretreatment removes all particulates. These fibers cannot be used in ultrafiltration applications at all. 

Spiral-wound modules are much more commonly used in low-pressure or vacuum gas separation applications, such as the production of oxygen-enriched air or the separation of organic vapors from air. In these applications, the feed gas is at close to ambient pressure, and a vacuum is drawn on the permeate side of the membrane. Parasitic pressure drops on the permeate side of the membrane and the difficulty in making high-performance hollow fine fiber membranes from the rubbery polymers used to make them both work against hollow fine fiber modules for such applications. 

Figure 4.13 A portion of the Wijmans plot shown in Figure 4.7 expanded to illustrate concentration polarization in some important gas separation applications...

Table 8.2 Module designs used for various gas separation applications...

Counterflow modules are always more efficient than crossflow modules, but the advantage is most noticeable when the membrane selectivity is much higher than the pressure ratio across the membrane and a significant fraction of the most permeable component is being removed from the feed gas. This is the case for air-dehydration membrane modules, so counterflow capillary modules are almost always used. With most other gas-separation applications, the advantage offered by counterflow designs does not offset the extra cost of making the counterflow type of module, so they are not widely used. 

Removal of impurities from natural gas is, by volume of gas to be treated, the largest gas-separation application [1, 17]. About 150 trillion scf of natural gas are produced each year worldwide. All of this gas requires some treatment before it can be used. So far, membranes have captured only 5% of this market, but the membrane share is growing currently, this is the fastest growing segment of the membrane... 

The problem with use of polymeric membranes in this application is plasticization, leading to much lower selectivities with gas mixtures than the simple ratio of pure-gas permeabilities would suggest. For this type of separation, a Robeson plot based on the ratio of pure-gas permeabilities has no predictive value. Although membranes with pure-gas propylene/propane selectivities of 20 or more have been reported [43, 44], only a handful of membranes have been able to achieve selectivities of 5 to 10 under realistic operating conditions, and these membranes have low permeances of 10 gpu or less for the fast component (propylene). This may be one of the few gas-separation applications where ceramic or carbon membranes have an industrial future. 

---