Hydrocarbon processing membranes

R.L. McKee, M.K. Changela and G.J. Reading, Carbon Dioxide Removal Membrane Plus Amine, Hydrocarbon Process. 70, 63 (1991). 

Depuis, G. E. et al., Hydrogen Membrane Recovery Estimates, Hydrocarbon Processing, pp. 61-64, Gulf Publishing Co., April 1993. 

In comparison, catalytic membrane reactors (CMRs) based upon OTM technology integrate oxygen separation from the atmosphere and hydrocarbon processing into a single exothermic step (see Fig. 7.1) ... 

W.J. Schell, and C. D. Houston, Process gas with selective membranes. Hydrocarbon Processing, Sept. 1982, 249-252. 

Accounts for the fact that feed gas contains some heavy hydrocarbons which membranes retain as a small extra benefit. Process details not specified standard cryogenic unit presumably considered. 

Figure 15-12. Flow diagram of reformer system with membrane hydrogen recovery unit on offgas (Yamashim eta ., 1988. Reproduced withpemisskm from Hydrocarbon Processing, Februaiy 1985...

R. McKee, CO2 removal membrane plus amine. Hydrocarbon Process, 1991, 70(4), 63-65. 

Membrane Pervaporation Since 1987, membrane pei vapora-tion has become widely accepted in the CPI as an effective means of separation and recovery of liquid-phase process streams. It is most commonly used to dehydrate hquid hydrocarbons to yield a high-purity ethanol, isopropanol, and ethylene glycol product. The method basically consists of a selec tively-permeable membrane layer separating a liquid feed stream and a gas phase permeate stream as shown in Fig. 25-19. The permeation rate and selectivity is governed bv the physicochemical composition of the membrane. Pei vaporation differs From reverse osmosis systems in that the permeate rate is not a function of osmotic pressure, since the permeate is maintained at saturation pressure (Ref. 24). 

A variety of ionomers have been described in the research literature, including copolymers of a) styrene with acrylic acid, b) ethyl acrylate with methacrylic acid, and (c) ethylene with methacrylic acid. A relatively recent development has been that of fluorinated sulfonate ionomers known as Nafions, a trade name of the Du Pont company. These ionomers have the general structure illustrated (10.1) and are used commercially as membranes. These ionomers are made by copolymerisation of the hydrocarbon or fluorocarbon monomers with minor amounts of the appropriate acid or ester. Copolymerisation is followed by either neutralisation or hydrolysis with a base, a process that may be carried out either in solution or in the melt. 

Whilst the basic process for generation and conversion of syngas is well established, production from biomass poses several challenges. These centre on the co-production of tars and hydrocarbons during the biomass gasification process, which is typically carried out at 800 °C. Recent advances in the production of more robust catalysts and catalytic membrane reactors should overcome many of these challenges. 

Studies of the effect of permeant s size on the translational diffusion in membranes suggest that a free-volume model is appropriate for the description of diffusion processes in the bilayers [93]. The dynamic motion of the chains of the membrane lipids and proteins may result in the formation of transient pockets of free volume or cavities into which a permeant molecule can enter. Diffusion occurs when a permeant jumps from a donor to an acceptor cavity. Results from recent molecular dynamics simulations suggest that the free volume transport mechanism is more likely to be operative in the core of the bilayer [84]. In the more ordered region of the bilayer, a kink shift diffusion mechanism is more likely to occur [84,94]. Kinks may be pictured as dynamic structural defects representing small, mobile free volumes in the hydrocarbon phase of the membrane, i.e., conformational kink g tg ) isomers of the hydrocarbon chains resulting from thermal motion [52] (Fig. 8). Small molecules can enter the small free volumes of the kinks and migrate across the membrane together with the kinks. 

The wastewater generated in the membrane cell and other process wastewaters in the cell are generally treated by neutralization.28 Other pollutants similar to those in mercury and diaphragm cells are treated in the same process stated above. Ion exchange and xanthate precipitation methods can be applied in this process to remove the metal pollutants, while incineration can be applied to eliminate some of the hydrocarbons. The use of modified diaphragms that resist corrosion and degradation will help in reducing the amount of lead, asbestos, and chlorinated hydrocarbon in the wastewater stream from the chlor-alkali industry.28... 

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