Reaction reforming

Steam reforming of CH is commonly carried out at 750 to 900°C, thus at the lower operating temperature of MCFCs a high activity catalyst is required. The internal reforming of methane in IRMCFCs, where the steam-reforming reaction... 

Naphtha desulfurization is conducted in the vapor phase as described for natural gas. Raw naphtha is preheated and vaporized in a separate furnace. If the sulfur content of the naphtha is very high, after Co—Mo hydrotreating, the naphtha is condensed, H2S is stripped out, and the residual H2S is adsorbed on ZnO. The primary reformer operates at conditions similar to those used with natural gas feed. The nickel catalyst, however, requires a promoter such as potassium in order to avoid carbon deposition at the practical levels of steam-to-carbon ratios of 3.5—5.0. Deposition of carbon from hydrocarbons cracking on the particles of the catalyst reduces the activity of the catalyst for the reforming and results in local uneven heating of the reformer tubes because the firing heat is not removed by the reforming reaction. 

Na.tura.1 Ga.s Reforma.tion. In the United States, most hydrogen is presently produced by natural gas reformation or methane—steam reforming. In this process, methane mixed with steam is typically passed over a nickel oxide catalyst at an elevated temperature. The reforming reaction is... 

Gas-Heated Reforming. Gas-heated reforming is an extension of the combined reforming concept where the primary reformer is replaced by a heat-transfer device in which heat for the primary reforming reaction is recovered from the secondary reformer effluent. Various mechanical designs have been proposed which are variants of a shell-and-tube heat exchanger (12,13). 

Secondary and tertiary amines are preferentially produced when rhodium or palladium are chosen as catalyst. As in Method 3, reforming reactions do not normally compete with the hydrogenation reaction and high selectivities to the desired product are possible. 

Thermal cracking tends to deposit carbon on the catalyst surface which can be removed by steaming. Carbon deposition by this mechanism tends to occur near the entrance of the catalyst tubes before sufficient hydrogen has been produced by the reforming reactions to suppress the right hand side of the reaction. Promoters, such as potash, are used to help suppress cracking in natural gas feedstocks containing heavier hydrocarbons. Carbon may also be formed by both the disproportionation and the reduction of carbon monoxide... 

Methanation. The methanation reactions are the reverse of the reforming reactions... 

In a typical PAFC system, methane passes through a reformer with steam from the coolant loop of the water-cooled fuel cell. Heat for the reforming reaction is generated by combusting the depleted fuel. The reformed natural gas contains typically 60 percent H9, 20 percent CO, and 20 percent H9O. Because the platinum catalyst in the PAFC can tolerate only about 0.5 percent CO, this fuel mixture is passed through a water gas shift reactor before being fed to the fuel cell. 

Thermodynamics of the water-gas shift and steam reforming reactions... 

In the steam reforming reaction, /rC02/p C0 = 2.08 (hr = 5.64) at this temperamre, and at lOOOK the results are hr A = 0.55 for carbon formation, and the PCO2/p CO ratio is 0.155 (hr A = 1.16), and tlrus the tendency for carbon formation passes from zero to unity in tlris temperature range. The presence of CO2 is not indicated in this reaction as given above, but its partial pressure can be obtained from data for the concunent reaction... 

Aside from the above reforming reactions, a small amount of feed components are converted to polymeric hydrogen deficient products which deposit on the catalyst as "coke." A coke buildup results in activity and selectivity loss which ultimately requires catalyst regeneration. In semi-regenerative operation, the coking rate is maintained at a low level to provide cycles of at least three to six months. In cyclic units, coking conditions are inherently much more severe so that frequent regenerations are required. 

Catalytic reformers are normally designed to have a series of catalyst beds (typically three beds). The first bed usually contains less catalyst than the other beds. This arrangement is important because the dehydrogenation of naphthenes to aromatics can reach equilibrium faster than the other reforming reactions. Dehydrocyclization is a slower reaction and may only reach equilibrium at the exit of the third reactor. Isomerization and hydrocracking reactions are slow. They have low equilibrium constants and may not reach equilibrium before exiting the reactor. 

In Europe, synthesis gas is mainly produced by steam reforming naphtha. Because naphtha is a mixture of hydrocarbons ranging approximately from C5-C10, the steam reforming reaction may be represented using n-heptane ... 

A promoted nickel type catalyst contained in the reactor tubes is used at temperature and pressure ranges of 700-800°C and 30-50 atmospheres, respectively. The reforming reaction is equilibrium limited. It is favored at high temperatures, low pressures, and a high steam to carbon ratio. These conditions minimize methane slip at the reformer outlet and yield an equilibrium mixture that is rich in hydrogen. ... 

Catalytic methanation is the reverse of the steam reforming reaction. Hydrogen reacts with carbon monoxide and carbon dioxide, converting them to methane. Methanation reactions are exothermic, and methane yield is favored at lower temperatures ... 

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