Separation of hydrogen

Graham showed that the rate of diffusion of different gases through a porous diaphragm was inversely proportional to the square roots of their densities this is the basis of a method of separation of gases, and has been applied successfully to the separation of hydrogen and deuterium. 

Additionally, there are a number of useful electrochemical reactions for desulfurization processes (185). Solar—thermal effusional separation of hydrogen from H2S has been proposed (188). The use of microporous Vicor membranes has been proposed to effect the separation of H2 from H2S at 1000°C. These membrane systems function on the principle of upsetting equiUbrium, resulting in a twofold increase in yield over equiUbrium amounts. 

Ceramic, Metal, and Liquid Membranes. The discussion so far implies that membrane materials are organic polymers and, in fact, the vast majority of membranes used commercially are polymer based. However, interest in membranes formed from less conventional materials has increased. Ceramic membranes, a special class of microporous membranes, are being used in ultrafHtration and microfiltration appHcations, for which solvent resistance and thermal stabHity are required. Dense metal membranes, particularly palladium membranes, are being considered for the separation of hydrogen from gas mixtures, and supported or emulsified Hquid films are being developed for coupled and facHitated transport processes. 

Table 4 summarizes commercial and precommercial gas separation appHcations (86,87). The first large-scale commercial appHcation of gas separation was the separation of hydrogen from nitrogen ia ammonia purge gas streams. This process, launched ia 1980 by Monsanto, was followed by a number of similar appHcations, such as hydrogen—methane separation ia refinery off-gases and hydrogen—carbon monoxide adjustment ia oxo-chemical synthetic plants. 

Dehydrogenation of isobutane to isobutylene is highly endothermic and the reactions are conducted at high temperatures (535—650°C) so the fuel consumption is sizeable. Eor the catalytic processes, the product separation section requires a compressor to facHitate the separation of hydrogen, methane, and other light hydrocarbons from-the paraffinic raw material and the olefinic product. An exceHent overview of butylenes is avaHable (81). 

A typical reactor operates at 600—900°C with no catalyst and a residence time of 10—12 s. It produces a 92—93% yield of carbon tetrachloride and tetrachloroethylene, based on the chlorine input. The principal steps in the process include (/) chlorination of the hydrocarbon (2) quenching of reactor effluents 3) separation of hydrogen chloride and chlorine (4) recycling of chlorine to the reactor and (i) distillation to separate reaction products from the hydrogen chloride by-product. Advantages of this process include the use of cheap raw materials, flexibiUty of the ratios of carbon tetrachloride and tetrachloroethylene produced, and utilization of waste chlorinated residues that are used as a feedstock to the reactor. The hydrogen chloride by-product can be recycled to an oxychlorination unit (30) or sold as anhydrous or aqueous hydrogen chloride. 

The gases are again dried and then further compressed to about 550 psi. Separation of hydrogen and methane take place in the demethanizer and in its preflash system. Three successive Golder preflash steps are used in this separation, with propylene as refrigerant, then ethylene, and finally a self-generated methane refrigerant at -200 F. 

The separation of hydrogen fluoride, HF (see Fig. 91, curve 20) occurs inversely to the separation of water, H20, (see Fig. 91, curve 18) the peak in HF separation corresponds to the minimum water concentration. Residual water that is usually adsorbed by the material and the surface of the inner parts of the vacuum cell clearly indicate the hydrolysis of the compounds. 

In gas separation with membranes, a gas mixture at an elevated pressure is passed across the surface of a membrane that is selectively permeable to one component of the mixture. The basic process is illustrated in Figure 16.4. Major current applications of gas separation membranes include the separation of hydrogen from nitrogen, argon and methane in ammonia plants the production of nitrogen from ah and the separation of carbon dioxide from methane in natural gas operations. Membrane gas separation is an area of considerable research interest and the number of applications is expanding rapidly. 

Figure 224. Separation process for enhancement of energy media transformation, (a) Schematic of the process, (A) an original equilibrium, (B) separation of hydrogen, (C) secondary equilibrium, (b) Relationship between separation process and reaction equilibrium line...

Cook WG, Ross RA. 1972. Gas-chromatographic separation of hydrogen sulfide, air, and water. Anal Chem 44 641-642. 

Hwang, G.-J. et al., Separation of hydrogen from a H2-H20-HI gaseous mixture using a silica membrane, AIChE., 46, 92,2000. 

Polymeric membranes, which offer bulk separation of hydrogen... 

Some of the polymeric membranes are suitable for bulk separation of hydrogen from impurities to enrich a dilute hydrogen stream. Dense polymers permeate gases by solution diffusion mechanism. The permeation rate of a gas species through a polymer membrane... 

Because Pd-alloy membranes operate at high temperatures in the range of WGS reaction and on the lower end of methane reforming reaction, they can be used in a membrane reactor configuration for the simultaneous separation of hydrogen. As discussed earlier,... 

Damle, A.S., Separation of Hydrogen and Carbon Dioxide in Advanced Fossil Energy Conversion Processes using a Membrane Reactor, 2002 Pittsburgh Coal Conference, Pittsburgh, PA, September 2002. 

Lin, Y.M. and M.H. Rei, Separation of hydrogen from the gas mixture out of a catalytic reformer by using supported palladium membrane, Sep. Purif. Technol., 25,87-95,2001a. 

Uemiya, S. et al., Separation of hydrogen through palladium thin film supported on a porous glass tube, /. Membr. Sci., 56, 303,1991a. 

Hydrogen-deuterium exchange Preparative separation of hydrogen isotopes. 

Table 8.4 Possible processes for heavy water production (Rae, H. K., Ed., Separation of hydrogen isotopes, ACS Symp. Ser. 68, 134 (1978)) ...

Diffusion.—The separation of hydrogen from the ler constituents of blue water gas has been proposed, iploying diffusion for the purpose. Graham expressed 2 law of diffusion of gases as. —... 

Cox et al. (1995) portray a new approach to thermochemical gasification of biomass to hydrogen. The process is based on catalytic steam gasification of biomass with concurrent separation of hydrogen in a membrane reactor that employs a permselective membrane to separate the hydrogen as it is produced. The process is particularly well-suited for wet biomass and may be conducted at temperatures as low as 575 K. 

Rae, H.K. "Selecting Heavy Water Processes" ACS Symposium Series No. 68, Separation of Hydrogen Isotopes, H.K. Rae (Editor). American Chemical Society, Washington, 1978... 

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