Steam reforming or steam methane reforming is a chemical synthesis for producing syngas, hydrogen, carbon monoxide from hydrocarbon fuels such as natural gas. This is achieved in a processing device called a reformer which reacts steam at high temperature and pressure with methane in the presence of a nickel catalyst. 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 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.
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.
Autothermal reforming (ATR) uses oxygen and carbon dioxide or steam in a reaction with methane to form syngas. The reaction takes place in a single chamber where the methane is partially oxidized. The reaction is exothermic due to the oxidation. When the ATR uses carbon dioxide the H2:CO ratio produced is 1:1; when the ATR uses steam the H2:CO ratio produced is 2.5:1
The reactions can be described in the following equations, using CO2:
And using steam:
The main difference between SMR and ATR is that SMR only uses oxygen via air for combustion as a heat source to create steam, while ATR directly combusts oxygen. The advantage of ATR is that the H2:CO can be varied, this is particularly useful for producing certain second generation biofuels, such as DME which requires a 1:1 H2:CO ratio.
Partial oxidation (POX) is a type of chemical reaction. It occurs when a substoichiometric fuel-air mixture is partially combusted in a reformer, creating a hydrogen-rich syngas which can then be put to further use.
The capital cost of steam reforming plants is prohibitive for small to medium size applications because the technology does not scale down well. Conventional steam reforming plants operate at pressures between 200 and 600 psi with outlet temperatures in the range of 815 to 925 °C. However, analyses have shown that even though it is more costly to construct, a well-designed SMR can produce hydrogen more cost-effectively than an ATR.
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:
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).
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.
However, there are several challenges associated with this technology:
The total hydrogen market was in 1998 390·10^9 Nm3/y + 110·10^9 Nm3/y co-production.