Primary reformer catalysts Reducibility

Decreased Firing in the Primary Reformer. Decreased heat supply in the primary reformer means that the process outlet temperature is lowered to about 700°C, the firing efficiency increases, and the size and cost of the primary reformer are reduced. The milder operating conditions prolong catalyst life, catalyst tube life, and outlet header service life.53... 

Catalyst makers also succeeded in minimizing the activity reducing effect of the potassium in the alkalized catalysts [430], Pre-reduced primary reforming catalysts are now also marketed (ICI Katalco, Topsoe) [430], and splitloading of reformer tubes with more than one type of catalyst has now become very common. The benefitial effects concern pressure drop at increased plant load, carbon formation potential, catalyst activity, catalyst cost, and desired catalyst life. For example, a reformer tube may be loaded with 15 % alkali-free catalyst in pre-reduced form (top-section), 25 % unreduced alkali-promoted (middle section) and 60% alkali-free unreduced catalyst (bottom section). 

From 1950, the demand for nitrogen fertilizers in North America led to the construction of many more ammonia plants all based on the steam reforming process. Modifications to the primary reforming catalysts by the incorporation of potash to reduce the level of caibon deposition have enabled operators in those parts of the World with no readily available supply of natural gas to use naphtha or refinery off-gases as feed for the primary reformer, and this has increased the versatility of the process even further. ... 

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. 

The steam requirements in an ammonia unit can be reduced by lowering the steam-to-carbon ratio to the primary reformer. However a number of drawbacks can exist downstream in the I I I S and LTS reactors. The drawbacks include By-product formation in the HTS, Pressure drop buildup in the HTS, Reversible poisoning of the LTS catalyst, and Higher CO equilibrium concentrations exiting the HTS and LTS reactors. 

ICI AMV Process. The ICI AMV process [1034], [1083], [1111] - [1122], also operates with reduced primary reforming (steam/carbon ratio 2.8) and a surplus of process air in the secondary reformer, which has a methane leakage of around 1 %. The nitrogen surplus is allowed to enter the synthesis loop, which operates at the very low pressure of 90 bar with an unusually large catalyst volume, the catalyst being a cobalt-enhanced version of the classical iron catalyst. The prototype was commissioned 1985 at Nitrogen Products (formerly CIL) in Canada, followed by additional plants in China. A flow sheet is shown in Figure 110. 

After desulfurization, steam is added and the mixture heated to 480 to 550°C before it is fed into the primary reformer. The gas leaving the primary reformer contains between 7 and 10% methane. This is removed in so-called secondary reformers in which the gas leaving the primary reformer is partially burnt with air in nickel catalyst-filled shaft furnaces (autothermal process), whereupon the temperature increases to ca. 1000°C. Under these conditions the methane reacts with the steam reducing the methane content in the synthesis gas to ca. 0.5 mole %. The quantity of air is adjusted to give the nitrogen to hydrogen ratio required for the stoichiometry of the ammonia synthesis. 

The profitability of this process is highly dependent on energy cost and capital investment. Energy and capital cost penalties associated with pollution control systems must therefore be minimized as far as practicable. The first step is to reduce the sulfur concentration in the ammonia plant feedstock to less than 0.1 ppmv to prevent poisoning the reformer catalyst. Once desulfurized, the feedstock is partially reacted with steam in a primary reformer to... 

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