Steam production, ammonia synthesis

High temperature steam reforming of natural gas accounts for 97% of the hydrogen used for ammonia synthesis in the United States. Hydrogen requirement for ammonia synthesis is about 336 m /t of ammonia produced for a typical 1000 t/d ammonia plant. The near-term demand for ammonia remains stagnant. Methanol production requires 560 m of hydrogen for each ton produced, based on a 2500-t/d methanol plant. Methanol demand is expected to increase in response to an increased use of the fuel—oxygenate methyl /-butyl ether (MTBE). 

Based on these developments, the foreseeable future sources of ammonia synthesis gas are expected to be mainly from steam reforming of natural gas, supplemented by associated gas from oil production, and hydrogen rich off-gases (especially from methanol plants). 

As mentioned in Chapter 2, methane is a one-carhon paraffinic hydrocarbon that is not very reactive under normal conditions. Only a few chemicals can he produced directly from methane under relatively severe conditions. Chlorination of methane is only possible by thermal or photochemical initiation. Methane can be partially oxidized with a limited amount of oxygen or in presence of steam to a synthesis gas mixture. Many chemicals can be produced from methane via the more reactive synthesis gas mixture. Synthesis gas is the precursor for two major chemicals, ammonia and methanol. Both compounds are the hosts for many important petrochemical products. Figure 5-1 shows the important chemicals based on methane, synthesis gas, methanol, and ammonia. ... 

In Europe naphtha is the preferred feedstock for the production of synthesis gas, which is used to synthesize methanol and ammonia (Chapter 4). Another important role for naphtha is its use as a feedstock for steam cracking units for light olefins production (Chapter 3). Heavy naphtha, on the other hand, is a major feedstock for catalytic reforming. The product reformate containing a high percentage of Ce-Cg aromatic hydrocarbons is used to make gasoline. Reformates are also extracted to separate the aromatics as intermediates for petrochemicals. 

If the rich gas from the CRG reactor is passed over another bed of high-nickel catalyst at a lower temperature, the equilibrium of the five components is reestablished. Carbon oxides react with hydrogen to form methane and the calorific value of the gas is increased. It should be noted that this methanation step differs from that encountered in ammonia synthesis gas production because of the high steam content the temperature rise is reduced and there is no possibility of temperature runaway as the... 

The reactor can operate with either a liquid-phase reaction or a gas-phase reaction. In both types, temperature is very important. With a gas-phase reaction, the operating pressure is also a critical design variable because the kinetic reaction rates in most gas-phase reactions depend on partial pressures of reactants and products. For example, in ammonia synthesis (N2 + 3H2 O 2NH3), the gas-phase reactor is operated at high pressure because of LeChatelier s principle, namely that reactions with a net decrease in moles should be mn at high pressure. The same principle leads to the conclusion that the steam-methane reforming reaction to form synthesis gas (CH4 + H20 O CO + 3 H2) should be conducted at low pressure. 

The ammonia loop is based on the Ammonia Casale axial-radial three-bed converter with internal heat exchangers. Heat from the ammonia synthesis is used to 1) generate high-pressure steam and 2) preheat feed gas. The gas is then cooled and refrigerated to separate ammonia product. Unconverted gas is recycled to the syngas compressor208 214... 

The present treatment of the conventional process will be based on the process diagram presented in Figure 1, which represents a steam reformer coupled with an ammonia synthesis plant [6], This is one of the two cases, which were considered in the project. The other was the use of the produced hydrogen as fuel in combined cycle gas turbines. In this chapter, the steam reforming part will be treated only, but some comments on the ammonia plant will be made, in view of the composition of the product stream leaving the steam reformer. 

Carbon monoxide, which is formed in the steam reforming reaction, deactivates the ammonia synthesis catalyst and must be removed by means of the exothermic water-gas shift reaction, which also maximises hydrogen production. To this end, CO is converted first to more easily removable CO2 ... 

Today, solid-catalyzed gas reactions are executed to an extent of several billions of tonnes per annum. To name only a few important examples Steam reforming of methane-rich natural gas to synthesis gas (H2 + CO), conversion of CO with H20 to C02 + H2, conversion of CO with H2 to methane, ammonia synthesis, oxidation of S02 to S03 (sulphuric acid production), oxidation of NH3 to NO (nitric acid production). The world production of ammonia in 1995 amounted to 90 m tonnes and... 

There are basically three processes in usage today for the production of hydrogen or ammonia synthesis gas Steam Reforming for the conversion of light hydrocarbons from natural gas to straight run naphthas Partial Oxidation for heavy hydrocarbons and coal and Electrolysis of Water. 

Assuming the feedstock is methane, which is the major component of natural gas, the theoretical feed requirement would be equivalent to one-fourth of the potential hydrogen production or 16,713 SCF CH /ST NH3(15.2 MM BTU/ST). However, the actual process consumes on the order of 22,420 SCF CHi+/ST NH3 or about 20.4 MM BTU/ST NH3 (LHV). The required quantity of feed depends on the process design criteria chosen for the methane conversion in the reforming section, the efficiency of CO conversion, degree of CO2 removal and the inerts (CHi+ + Ar) level maintained in the ammonia synthesis loop. Thus, the potential hydrogen conversion efficiency of the feedstock in the steam reforming process is about 75%. Table 3 shows where the balance of the feed is consumed or lost from the process. 

The purified gas is fed into the Synthol and fixed-bed reactors. The products from the reactors are cooied and separated in a water phase, oil phase and tail gas. The + Ca olefinic products from the tail gas are separated in an oil absorption tower and oligomerized over an acidic catalyst to gasoline. Tite remaining tali gas can be treated in a cryogenic unit to provide methane and hydrogen, which is partly used as fuel gas or feedstock for ammonia synthesis. The remainder is steam-reformed over nickel catalysts to give CO/H3. 

Hydrogen and Carbon Dioxide Production from Steam-Methane Reformer Off Gas Production of Ammonia Synthesis Gas Hydrogen Recovery fiom Refinery Off Gases Methane-Carbon Dioxide Separation from Landfill Gas... 

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