Secondary reformer catalysts

The secondary reformer catalyst does not need to be as active as that in the primary reformer. The usual nickel concentration is about 15 percent in the secondary reformer and 25 percent in the primary reformer catalyst. 

Secondary reforming catalyst contains about 7% nickel oxide, supported on temperature-resistant a-alumina or calcium aluminate, in the form of raschig rings. Additional catalyst used at the top of the bed as a heat guard is in the form of large solid cylinders of a-alumina containing 5% nickel oxide. 

MPa (300—400 psig), using a Ni-based catalyst. Temperatures up to 1000°C and pressures up to 3.79 MPa (550 psia) are used in an autothermal-type reformer, or secondary reformer, when the hydrogen is used for ammonia, or in some cases methanol, production. 

Reforming is completed in a secondary reformer, where air is added both to elevate the temperature by partial combustion of the gas stream and to produce the 3 1 H2 N2 ratio downstream of the shift converter as is required for ammonia synthesis. The water gas shift converter then produces more H2 from carbon monoxide and water. A low temperature shift process using a zinc—chromium—copper oxide catalyst has replaced the earlier iron oxide-catalyzed high temperature system. The majority of the CO2 is then removed. 

Ammonia production from natural gas includes the following processes desulfurization of the feedstock primary and secondary reforming carbon monoxide shift conversion and removal of carbon dioxide, which can be used for urea manufacture methanation and ammonia synthesis. Catalysts used in the process may include cobalt, molybdenum, nickel, iron oxide/chromium oxide, copper oxide/zinc oxide, and iron. 

Figure 8.3.1 is a typical process diagram for tlie production of ammonia by steam reforming. Tlie first step in tlie preparation of tlie synthesis gas is desulfurization of the hydrocarbon feed. Tliis is necessary because sulfur poisons tlie nickel catalyst (albeit reversibly) in tlie reformers, even at very low concentrations. Steam reforming of hydrocarbon feedstock is carried out in tlie priiiiiiry and secondary reformers. 

The second step after secondary reforming is removing carbon monoxide, which poisons the catalyst used for ammonia synthesis. This is done in three further steps, shift conversion, carbon dioxide removal, and methanation of the remaining CO and CO2. 

Composition of Some Industrial Steam Reforming Catalysts (NG = natural gas, HC = hydrocarbon, PR = prereforming, LPG = liquefied petroleum gas, SEC = secondary reforming)... 

In ammonia plants, the secondary reformer is included to decrease further the proportion of methane in the final gas and also to introduce the required amount of nitrogen for ammonia synthesis. The bed temperature is maintained at 1000 °C and this is achieved by adding air to the gas stream, the oxygen of the air reacting with the hydrogen of the gas stream to form water. The reactor consists of a packed bed and no additional heating is required. The exit gas contains less than 0.1% CH4. The catalyst for this reactor does not require to have very high activity but it must be stable under these reaction conditions. 

Natural gas is desulfurized because sulfur has an adverse effect on the catalysts used in the reforming and synthesis reactions. After desulfurization and scrubbing, the natural gas is mixed with superheated steam at 23 barg and 510°C. Nitrogen is supplied from the air, which is fed to the secondary reformer at 20 barg and 166°C. Table 5 shows the composition of air. 

Steam reforming refers to the endothermic, catalytic conversion of light hydrocarbons (methane to gasoline) in the presence of steam [see Eq. (5.1)]. The reforming reaction takes place across a nickel catalyst that is packed in tubes in an externally-fired, tubular furnace (the Primary Reformer). The lined chamber reactor is called the secondary reformer , and this is where hot process air is added to introduce nitrogen into the process. Typical reaction conditions in the Primary Reformer are 700°C to 830°C and 15 to 40 bar46. 

Although silica and silica-bearing materials are very useful in making catalyst supports, they cannot be used for the shift catalyst. This is because the silica volatilizes and migrates from the hotter zone to lower temperature zones downstream. Usually it deposits on the waste heat boiler tubes after the secondary reformer. 

The secondary reformer vessel is a refractory-lined vessel that has an oxygen burner in its top neck and a fixed catalyst bed. Installation of a secondary reformer usually requires significant changes to the CO2 removal system Hydrogen purity can be increased up to 98%. The economics generally depend on a reliable source of low-cost oxygen172. 

In 2001 Hyprotech and Synetix announced an ammonia plant simulation that can be used for modeling, on-line monitoring and optimization of the plant. The simulation includes Synetix reactor models, customized thermodynamic data and information to simulate the performance of a range of catalysts. The reactor models in the simulation include Primary and Secondary Reformers, High Temperature Shift converter, Low Temperature Shift Converter, Methanator and Ammonia Synthesis Converter80. 

The reforming process is completed in the authothermic secondary reformer, which is a refractory lined vessel containing a fixed-bed catalyst. The remainder of the endothermic heat requirement is provided by the combustion of part of the primary reformer effluent directly with air. This allows much higher process temperatures, of the order of 1000°C, to be attained at the secondary reformer exit and consequently low methane slips in the range of 0.2-... 

In an ammonia plant (Figure 4.2), the synthesis gas from the reformer furnace is fed into a secondary reformer vessel, where air is added through a burner to create outlet vessel temperatures of -1,800° F (980° C). The outlet of the secondary reformer vessel is cooled in a quench steam generator and sent to a shift converter this is followed by a carbon dioxide removal system such as the one in a hydrogen plant. The purified nitrogen from the air added in the secondary reformer vessel and hydrogen synthesis gas is fed to a methanator to convert residual oxides of carbon back to methane (which is inert in the ammonia conversion) the gas is then compressed to -3,000 psia (2,070 kPa). The compressed synthesis gas is fed to an ammonia converter vessel. As the synthesis gas passes over catalyst beds, ammonia is formed. The ammonia product is then cooled and refrigerated to separate out impurities. 

Description The key features of the KBR Purifier Process are mild primary reforming, secondary reforming with excess air, cryogenic purification of syngas, and synthesis of ammonia over magnetite catalyst in a horizontal converter. 

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