Thermodynamics methanation

Conformational free energy simulations are being widely used in modeling of complex molecular systems [1]. Recent examples of applications include study of torsions in n-butane [2] and peptide sidechains [3, 4], as well as aggregation of methane [5] and a helix bundle protein in water [6]. Calculating free energy differences between molecular states is valuable because they are observable thermodynamic quantities, related to equilibrium constants and... 

Many simple systems that could be expected to form ideal Hquid mixtures are reasonably predicted by extending pure-species adsorption equiUbrium data to a multicomponent equation. The potential theory has been extended to binary mixtures of several hydrocarbons on activated carbon by assuming an ideal mixture (99) and to hydrocarbons on activated carbon and carbon molecular sieves, and to O2 and N2 on 5A and lOX zeoHtes (100). Mixture isotherms predicted by lAST agree with experimental data for methane + ethane and for ethylene + CO2 on activated carbon, and for CO + O2 and for propane + propylene on siUca gel (36). A statistical thermodynamic model has been successfully appHed to equiUbrium isotherms of several nonpolar species on 5A zeoHte, to predict multicomponent sorption equiUbria from the Henry constants for the pure components (26). A set of equations that incorporate surface heterogeneity into the lAST model provides a means for predicting multicomponent equiUbria, but the agreement is only good up to 50% surface saturation (9). 

Thermodynamically, the formation of methane is favored at low temperatures. The equilibrium constant is 10 at 300 K and is 10 ° at 1000 K (113). High temperatures and catalysts ate needed to achieve appreciable rates of carbon gasification, however. This reaction was studied in the range 820—1020 K, and it was found that nickel catalysts speed the reaction by three to four orders of magnitude (114). The Hterature for the carbon-hydrogen reaction has been surveyed (115). 

The process gas of ethylene plants and methyl tertiary butyl ether plants is normally a hydrogen/ methane mixture. The molecular weight of the gas in such processes ranges from 3.5 to 14. The tliermodynamic behavior of hydrogen/methane mixtures has been and continues to be extensively researched. The gas dynamic design of turboexpanders, which are extensively used in such plants, depends on the equations of state of the process gas. Optimum performance of the turboexpander and associated equipment demands accurate thermodynamic properties for a wide range of process gas conditions. 

Adsorption of hard sphere fluid mixtures in disordered hard sphere matrices has not been studied profoundly and the accuracy of the ROZ-type theory in the description of the structure and thermodynamics of simple mixtures is difficult to discuss. Adsorption of mixtures consisting of argon with ethane and methane in a matrix mimicking silica xerogel has been simulated by Kaminsky and Monson [42,43] in the framework of the Lennard-Jones model. A comparison with experimentally measured properties has also been performed. However, we are not aware of similar studies for simpler hard sphere mixtures, but the work from our laboratory has focused on a two-dimensional partly quenched model of hard discs [44]. That makes it impossible to judge the accuracy of theoretical approaches even for simple binary mixtures in disordered microporous media. 

Methane is unique among hydrocarbons in being thermodynamically stable with respect to its elements. It follows that pyrolytic reactions to convert it to other hydrocarbons are energetically unfavourable and will be strongly equilibrium-limited. This is in marked contrast to the boranes where mild thermolysis of B2H6 or B4H10, for example, readily yields mixtures of the higher boranes (p. 164). Vast natural reserves of CH4 gas exist but much is wasted... 

Examine the structures of the two transition states (chlorine atom+methane and chlorine+methyI radical). For each, characterize the transition state as early (close to the geometry of the reactants) or as late (close to the geometry of the products) In Ught of the thermodynamics of the individual steps, are your results anticipated by the Hammond Postulate Explain. 

Alpha-scission is not favored thermodynamically but does occur. Alpha-scission produces a methyl radical, which can extract a hydrogen atom from a neutral hydrocarbon molecule. The hydrogen extraction produces methane and a secondary or tertiary free radical (Equation 4-3). 

This paper surveys the field of methanation from fundamentals through commercial application. Thermodynamic data are used to predict the effects of temperature, pressure, number of equilibrium reaction stages, and feed composition on methane yield. Mechanisms and proposed kinetic equations are reviewed. These equations cannot prove any one mechanism however, they give insight on relative catalyst activity and rate-controlling steps. Derivation of kinetic equations from the temperature profile in an adiabatic flow system is illustrated. Various catalysts and their preparation are discussed. Nickel seems best nickel catalysts apparently have active sites with AF 3 kcal which accounts for observed poisoning by sulfur and steam. Carbon laydown is thermodynamically possible in a methanator, but it can be avoided kinetically by proper catalyst selection. Proposed commercial methanation systems are reviewed. 

Chemistry and Thermodynamics. The principal reactions which occur in the methanation process are ... 

Carbon Laydown. The potential for carbon laydown is readily estimated from the thermodynamics of Reactions 4 and 5. The areas where carbon laydown, according to these reactions, is thermodynamically possible were developed by Gruber (36). It is readily seen that carbon laydown via Reaction 4 is thermodynamically favorable at the reactor inlet for practically any commercially conceivable feed gas composition. As noted by Gruber (36), carbon laydown is thermodynamically unfavorable at the reactor outlet for practically all commercially conceivable methanator conditions. The methanation reactor will therefore, in practice, have two zones—the first is a finite zone between the inlet and some way down the catalyst bed where carbon laydown is thermodynamically possible, and the second zone is the balance of the reactor. 

Steam-Moderated Process. The basic idea behind this approach is to limit the extent of conversion of the methanation reaction, Reaction 1, by adding steam to the feed gases. This process simultaneously provides for (46) elimination of the CO shift, Reaction 2, to get a 3 1 H2 CO ratio from the make-up gas ratio of about 1.5 1 and avoidance of carbon laydown by operation under conditions in which carbon is not a thermodynamically stable phase (see Chemistry and Thermodynamics section above). 

The scheme of commercial methane synthesis includes a multistage reaction system and recycle of product gas. Adiabatic reactors connected with waste heat boilers are used to remove the heat in the form of high pressure steam. In designing the pilot plants, major emphasis was placed on the design of the catalytic reactor system. Thermodynamic parameters (composition of feed gas, temperature, temperature rise, pressure, etc.) as well as hydrodynamic parameters (bed depth, linear velocity, catalyst pellet size, etc.) are identical to those in a commercial methana-tion plant. This permits direct upscaling of test results to commercial size reactors because radial gradients are not present in an adiabatic shift reactor. 

The series of reactors and exchangers which methanates a raw syngas without pretreatment other than desulfurization is collectively termed bulk methanation. The chemical reactions which occur in bulk methana-tion, including both shift conversion and methanation, are moderated by the addition of steam which establishes the thermodynamic limits for these reactions and thereby controls operating temperatures. The flow sequence through bulk methanation is shown in Figure 1. 

Dr. Woodward May I just make one comment to emphasize and to repeat what was said earlier Thermodynamics and kinetics. Yes, under the inlet conditions of several SNG processes, and also of methanation in ammonia and hydrogen processes, thermodynamically they are inside the carbon-forming region. At the exit they tend not to be. In practice, carbon is not formed. One could, therefore, conclude very simply that kinetics outweighs thermodynamics. 

The various processes involving carbon monoxide steam reforming, water-gas shift, methanation, and methanol synthesis illustrate the operation of thermodynamic constraints and some of their attendant economic consequences. 

The thermodynamic properties of a chemical substance are dependent upon its state and, therefore, it is important to indicate conditions when writing chemical reactions. For example, in the burning of methane to form carbon dioxide and water, it is important to specify whether each reactant and product are solid, liquid, or gaseous since different changes in the thermodynamic property will occur depending upon the state of each substance. Thus, different volume and energy changes occur in the reactions... 

Fuel cells such as the one shown on Fig. 3.4a convert H2 to H20 and produce electrical power with no intermediate combustion cycle. Thus their thermodynamic efficiency compares favorably with thermal power generation which is limited by Carnot-type constraints. One important advantage of solid electrolyte fuel cells is that, due to their high operating temperature (typically 700° to 1100°C), they offer the possibility of "internal reforming" which permits the use of fuels such as methane without a separate external reformer.33 36... 

Rh(TMP)- under these conditions, and in fact the selective activation of methane in benzene solution is a distinctive and unusual feature of this system, given that aryl C—H activation ought to be thermodynamically favored over alkyl C—H activation. The proposed linear transition state proposed in Fig. 8 is the key to this different reactivity. The corresponding trimolecular transition state for an arene would be expected to be bent, and this would be precluded by the bulky TMP... 

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