Syngas

Syngas (Synthesis gas) is the name given to a gas mixture that contains varying amounts of carbon monoxide and hydrogen. Examples of production methods include steam reforming of natural gas or liquid hydrocarbons to produce hydrogen, the gasification of coal, biomass, and in some types of waste-to-energy gasification facilities. The name comes from their use as intermediates in creating synthetic natural gas (SNG) and for producing ammonia or methanol. Syngas is also used as an intermediate in producing synthetic petroleum for use as a fuel or lubricant via the Fischer–Tropsch process and previously the Mobil methanol to gasoline process.

Syngas consists primarily of hydrogen, carbon monoxide, and very often some carbon dioxide, and has less than half the energy density of natural gas. The main reaction that produces syngas, steam reforming, is endothermic with 206 kJ/mol methane needed for conversion. Syngas is combustible and often used as a fuel of internal combustion engines or as an intermediate for the production of other chemicals.

Production

Syngas for use as a fuel is most often produced from coal or from biomass or municipal waste, first by pyrolysis to coke (impure carbon), aka destructive distillation, followed by alternating blasts of steam and air mainly by the following simple paths:

C + H₂O → CO + H₂

∆H°298 = 175.3 kJ/mol

C + O₂ → CO₂

∆H°298 = -393.5 kJ/mol

CO₂ + C → 2CO

∆H°298 = 172.5 kJ/mol

The first reaction, between incandescent coke and steam, is strongly endothermic, producing carbon monoxide (CO), and hydrogen H₂ (water gas in older terminology).

When the coke bed has cooled to a temperature at which the endothermic reaction can no longer proceed, the steam is then replaced by a blast of air.

The second and third reactions then take place, producing an exothermic reaction - forming initially carbon dioxide - raising the temperature of the coke bed - followed by the second endothermic reaction, in which the latter is converted to carbon monoxide, CO. The overall reaction is exothermic, forming "producer gas" (older terminology). Steam can then be re-injected, then air etc., to give an endless series of cycles until the coke is finally consumed. Producer gas has a much lower energy value, relative to water gas, due primarily to dilution with atmospheric nitrogen. Pure oxygen can be substituted for air to avoid the dilution effect, producing gas of much higher calorific value.

When used as an intermediate in the large-scale, industrial synthesis of hydrogen (principally used in the production of ammonia), it is also produced from natural gas (via the steam reforming reaction) as follows:

CH₄ + H₂O → CO + 3 H₂

In order to produce more hydrogen from this mixture, more steam is added and the water gas shift reaction is carried out:

CO + H₂O → CO₂ + H₂

The hydrogen must be separated from the CO₂ to be able to use it. This is primarily done by pressure swing adsorption (PSA), amine scrubbing, and membrane reactors.

Alternative technologies

Biomass catalytic partial oxidation

Conversion of biomass to syngas is typically low-yield. The University of Minnesota developed a metal catalyst that reduces the biomass reaction time by up to a factor of 100. The catalyst can be operated at atmospheric pressure and reduces char. The entire process is autothermic and therefore heating is not required.

Using solar energy

Besides using coal to generate the heat, the power of the sun can also be used.

The syngas produced in waste-to-energy gasification facilities can be used to generate electricity.

Coal gasification processes were used for many years to manufacture illuminating gas (coal gas) for gas lighting, cooking and to some extent, heating, before electric lighting and the natural gas infrastructure became widely available.

Post-treatment

Syngas can be used in the Fischer–Tropsch process to produce diesel, or converted into e.g. methane, methanol, and dimethyl ether in catalytic processes.

If the syngas is post-treated by cryogenic processing, it should be taken into account that this technology has great difficulty in recovering pure carbon monoxide if relatively large volumes of nitrogen are present due to carbon monoxide and nitrogen having very similar boiling points which are -191.5 °C and -195.79 °C respectively. Certain process technology selectively removes carbon monoxide by complexation/decomplexation of carbon monoxide with cuprous aluminum chloride (CuAlCl₄), dissolved in an organic liquid, such as toluene. The purified carbon monoxide can have a purity greater than 99%, which makes it a good feedstock for the chemical industry. The reject gas from the system can contain carbon dioxide, nitrogen, methane, ethane, and hydrogen. The reject gas can be further processed on a pressure swing adsorption system to remove hydrogen, and the hydrogen and carbon monoxide can be recombined in the proper ratio for catalytic methanol production, Fischer-Tropsch diesel, etc. Cryogenic purification, being very energy intensive, is not well suited to simply making fuel, because of the greatly reduced net energy gain.^{[citation needed]}

Energy capacity

Syngas that is not methanized typically has a specific heat capacity of 120 BTU/scf. Untreated syngas can be run in hybrid turbines that allow for greater efficiency because of their lower operating temperatures, and extended part lifetime.

See also

• Ammonia
• Biochar
• Boudouard reaction
• Carbon monoxide
• Dimethyl ether
• Integrated gasification combined cycle
• Gasification
• Methane
• Methanol
• Partial oxidation
• Producer gas
• Reformer sponge iron cycle
• Syngas fermentation
• Town gas
• Underground coal gasification
• Water gas
• Wood gas

External links

• Fischer Tropsch archive

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