Methane in methanation

Muller U, Hesse M, Puetter H, Wessel H. Adsorptive anreicherung von methan in methan-haltigen gasgemischen. Patent EP 1,674,555 2005. 

The critical temperature of methane is 191°K. At 25°C, therefore, the reduced temperature is 1.56. If the dividing line is taken at T/T = 1.8, methane should be considered condensable at temperatures below (about) 70°C and noncondensable at higher temperatures. However, in process design calculations, it is often inconvenient to switch from one method of normalization to the other. In this monograph, since we consider only equilibria at low or moderate pressures in the region 200-600°K, we elect to consider methane as a noncondensable component. 

Table 3 shows results obtained from a five-component, isothermal flash calculation. In this system there are two condensable components (acetone and benzene) and three noncondensable components (hydrogen, carbon monoxide, and methane). Henry s constants for each of the noncondensables were obtained from Equations (18-22) the simplifying assumption for dilute solutions [Equation (17)] was also used for each of the noncondensables. Activity coefficients for both condensable components were calculated with the UNIQUAC equation. For that calculation, all liquid-phase composition variables are on a solute-free basis the only required binary parameters are those for the acetone-benzene system. While no experimental data are available for comparison, the calculated results are probably reliable because all simplifying assumptions are reasonable the... 

The secondary reactions are series with respect to the chloromethane but parallel with respect to chlorine. A very large excess of methane (mole ratio of methane to chlorine on the order of 10 1) is used to suppress selectivity losses. The excess of methane has two effects. First, because it is only involved in the primary reaction, it encourages the primary reaction. Second, by diluting the product, chloromethane, it discourages the secondary reactions, which prefer a high concentration of chloromethane. 

Many processes, particularly in the petrochemical industries, produce a reactor efiiuent which consists of a mixture of low-boiling components such as hydrogen and methane together with much less... 

The reactor effluent is thus likely to contain hydrogen, methane, benzene, toluene, and diphenyl. Because of the large differences in volatility of these components, it seems likely that partial condensation will allow the effluent to be split into a vapor stream containing predominantly hydrogen and methane and a liquid stream containing predominantly benzene, toluene, and diphenyl. 

The hydrogen in the vapor stream is a reactant and hence should be recycled to the reactor inlet (Fig. 4.8). The methane enters the process as a feed impurity and is also a byproduct from the primary reaction and must be removed from the process. The hydrogen-methane separation is likely to be expensive, but the methane can be removed from the process by means of a purge (see Fig. 4.8). 

Determine the relation between the fraction of vapor from the phase split sent to purge (a) and the fraction of methane in the recycle and purge (y). 

Figure 4.9 shows a plot of Eq. (4.12). As the purge fraction a is increased, the flow rate of purge increases, but the concentration of methane in the purge and recycle decreases. This variation (along with reactor conversion) is an important degree of freedom in the optimization of reaction and separation systems, as we shall see later. 

Mole fraction of methane in vapor from phase separator = 0.4... 

Given the estimate of the reactor effluent in Example 4.2 for fraction of methane in the purge of 0.4, calculate the.actual separation in the phase split assuming a temperature in the phase separator of 40°C. Phase equilibrium for this mixture can be represented by the Soave-Redlich-Kwong equation of state. Many computer programs are available commercially to carry out such calculations. 

The temperature of the phase split is well above the critical temperatures of both hydrogen and methane, leading to large K values. On the other hand, the K values of the benzene, toluene, and diphenyl are very low, and hence the assumption of a sharp split in Example 4.2 was a good one. 

One advantage of anaerobic reactions is that the methane produced can be a useful source of energy. This can be fed to steam boilers or burnt in a heat engine to produce power. 

Figure 14.8a shows a simplified flowsheet for the manufacture of acetic anhydride as presented by Jeffries. Acetone feed is cracked in a furnace to ketene and the byproduct methane. The methane is used as furnace fuel. A second reactor forms acetic anhydride by the reaction between ketene from the first reaction and acetic acid. 

HOCH2CH2CH2CH2OH. B.p. 228"C. Prepared ethyne plus methanal, hydrogenated to butanediol. Used in production of y-buty-rolactone and 2-pyrrolidone. Widely used in polyurethane products, butylenes See butenes. 

HOCH2C = CCH2OH. White solid, m.p. 58 C, b.p. 238- C prepared by the high pressure reaction between ethyne and methanol and also from BrMgCCMgBr and methanal. Used in electroplating (Ni), as a corrosion inhibitor, and in paint and varnish removal. 

Claisen reaction Condensation of an aldehyde with another aldehyde or a ketone in the presence of sodium hydroxide with the elimination of water. Thus benzaldehyde and methanal give cinnamic aldehyde, PhCH CH-CHO. 

The original method for the manufacture of ethyne, the action of water on calcium carbide, is still of very great importance, but newer methods include the pyrolysis of the lower paraffins in the presence of steam, the partial oxidation of natural gas (methane) and the cracking of hydrocarbons in an electric arc. 

If air (or oxygen) and steam are both passed through a high-temperature bed of coal or coke these reactions can be balanced, thus controlling the bed temperature and the fusion of the ash. In the higher pressure Lurgi process the gas obtained is high in methane, formed in reactions such as... 

Covalent. Formed by most of the non-metals and transition metals. This class includes such diverse compounds as methane, CH4 and iron carbonyl hydride, H2Fe(CO)4. In many compounds the hydrogen atoms act as bridges. Where there are more than one hydride sites there is often hydrogen exchange between the sites. Hydrogens may be inside metal clusters. 

A mixture of polymethylene glycols of the type (CH20) ,xH20 where n is 6- 50. It is a white, amorphous powder having the odour of meth-anal, m.p. I20-130°C. The commercial product contains 95% methanal and is obtained in while flocculent masses when solutions of methanal are evaporated or allowed to stand. When heated it is converted to methanal. Used as a convenient solid substitute for methanal. 

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