Steam reforming is a method for producing hydrogen, carbon monoxide, or other useful products from hydrocarbon fuels such as natural gas. This is achieved in a processing device called a reformer which reacts steam at high temperature with the fossil fuel. The steam methane reformer is widely used in industry to make hydrogen. There is also interest in the development of much smaller units based on similar technology to produce hydrogen as a feedstock for fuel cells. Small-scale steam reforming units to supply fuel cells are currently the subject of research and development, typically involving the reforming of methanol, but other fuels are also being considered such as propane, gasoline, autogas, diesel fuel, and ethanol.
Steam reforming of natural gas - sometimes referred to as steam methane reforming (SMR) - is the most common method of producing commercial bulk hydrogen at about 95% of the world production of 500 billion m3 in 1998. Hydrogen is used in the industrial synthesis of ammonia and other chemicals. At high temperatures (700 – 1100 °C) and in the presence of a metal-based catalyst (nickel), steam reacts with methane to yield carbon monoxide and hydrogen.
Catalysts with high surface-area-to-volume ratio are preferred because of diffusion limitations due to high operating temperature. Examples of catalyst shapes used are spoked wheels, gear wheels, and rings with holes. Additionally, these shapes have a low pressure drop which is advantageous for this application.
- CO + H2O ⇌ CO2 + H2
The United States produces nine million tons of hydrogen per year, mostly with steam reforming of natural gas. The worldwide ammonia production, using hydrogen derived from steam reforming, was 144 million metric tonnes in 2014.
This steam reforming process is quite different from and not to be confused with catalytic reforming of naphtha, an oil refinery process that also produces significant amounts of hydrogen along with high octane gasoline.
Steam reforming of natural gas is approximately 65–75% efficient.
Reforming for combustion engines
Flared gas and vented VOCs are known problems in the offshore industry and in the on-shore oil and gas industry, since both emit unnecessary greenhouse gases into the atmosphere. Reforming for combustion engines utilizes steam reforming technology for converting waste gases into a source of energy.
Reforming for combustion engines is based on steam reforming, where non-methane hydrocarbons (NMHCs) of low quality gases are converted to synthesis gas (H2 + CO) and finally to methane (CH4), carbon dioxide (CO2) and hydrogen (H2) - thereby improving the fuel gas quality (methane number).
In contrast to conventional steam reforming, the process is operated at lower temperatures and with lower steam supply, allowing a high content of methane (CH4) in the produced fuel gas. The main reactions are:
- CnHm + n H2O ⇌ (n + m⁄2) H2 + n CO
- CO + 3 H2 ⇌ CH4 + H2O
- CO + H2O ⇌ H2 + CO2
Reforming for fuel cells
Advantages of reforming for supplying fuel cells
Steam reforming of gaseous hydrocarbons is seen as a potential way to provide fuel for fuel cells. The basic idea for vehicle on-board reforming is that for example a methanol tank and a steam reforming unit would replace the bulky pressurized hydrogen tanks that would otherwise be necessary. This might mitigate the distribution problems associated with hydrogen vehicles; however the major market players discarded the approach of on-board reforming as impractical. (At high temperatures see above).
Disadvantages of reforming for supplying fuel cells
The reformer–fuel-cell system is still being researched but in the near term, systems would continue to run on existing fuels, such as natural gas or gasoline or diesel. However, there is an active debate about whether using these fuels to make hydrogen is beneficial while global warming is an issue. Fossil fuel reforming does not eliminate carbon dioxide release into the atmosphere but reduces the carbon dioxide emissions and nearly eliminates carbon monoxide emissions as compared to the burning of conventional fuels due to increased efficiency and fuel cell characteristics. However, by turning the release of carbon dioxide into a point source rather than distributed release, carbon capture and storage becomes a possibility, which would prevent the carbon dioxide's release to the atmosphere, while adding to the cost of the process.
The cost of hydrogen production by reforming fossil fuels depends on the scale at which it is done, the capital cost of the reformer and the efficiency of the unit, so that whilst it may cost only a few dollars per kilogram of hydrogen at industrial scale, it could be more expensive at the smaller scale needed for fuel cells.
Current challenges with reformers supplying fuel cells
However, there are several challenges associated with this technology:
- The reforming reaction takes place at high temperatures, making it slow to start up and requiring costly high temperature materials.
- Sulfur compounds in the fuel will poison certain catalysts, making it difficult to run this type of system from ordinary gasoline. Some new technologies have overcome this challenge with sulfur-tolerant catalysts.
- Coking would be another cause of catalyst deactivation during steam reforming. High reaction temperatures, low steam-to-carbon ratio (S/C), and the complex nature of sulfur-containing commercial hydrocarbon fuels make coking especially favorable. Olefins, typically ethylene, and aromatics are well known carbon-precursors, hence their formation must be reduced during the SR. Additionally, catalysts with lower acidity were reported to be less prone to coking by suppressing dehydrogenation reactions. H2S, the main product in the reforming of organic sulfur, can bind to all transition metal catalysts to form metal–sulfur bonds and subsequently reduce catalyst activity by inhibiting the chemisorption of reforming reactants. Meanwhile, the adsorbed sulfur species increases the catalyst acidity, and hence indirectly promotes coking. Precious metal catalysts such as Rh and Pt have lower tendencies to form bulk sulfides than other metal catalysts such as Ni. Rh and Pt are less prone to sulfur poisoning by only chemisorbing sulfur rather than forming metal sulfides.
- Low temperature polymer fuel cell membranes can be poisoned by the carbon monoxide (CO) produced by the reactor, making it necessary to include complex CO-removal systems. Solid oxide fuel cells (SOFC) and molten carbonate fuel cells (MCFC) do not have this problem, but operate at higher temperatures, slowing start-up time, and requiring costly materials and bulky insulation.
- The thermodynamic efficiency of the process is between 70% and 85% (LHV basis) depending on the purity of the hydrogen product.
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