Upgradation of biogas is primarily achieved by carbon dioxide removal which then enhances the energy value of the gas to give longer, driving distances with a fixed gas storage volume. Removal of carbon dioxide also provides a consistent gas quality with respect to energy value. The latter is regarded to be of great importance from the vehicle manufacturers in order to reach low emissions of nitrogen oxide.
At present four different methods are commercially used for removal of carbon dioxide from biogas, either to reach vehicle fuel standard or to reach natural gas quality for injection to the natural gas grid. These methods are:
- Water absorption
- Polyethylene glycol absorption
- Carbon molecular sieves
- Membrane separation
Water scrubbing is used to remove carbon dioxide but also hydrogen sulphide from biogas since these gases is more soluble in water than methane. The absorption process is purely physical. Usually the biogas is pressurized and fed to the bottom of a packed column where water is fed on the top and so the absorption process is operated counter-currently.
Polyethylene Glycol Scrubbing
Polyethylene glycol scrubbing is a physical absorption process. Selexol is one of the trade names used for a solvent. In this solvent, like in water, both carbon dioxide and hydrogen sulphide are more soluble than methane.
The big difference between water and Selexol is that carbon dioxide and hydrogen sulphide are more soluble in Selexol which results in a lower solvent demand and reduced pumping. In addition, water and halogenated hydrocarbons (contaminants in biogas from landfills) are removed when scrubbing biogas with Selexol.
Carbon Molecular Sieves
Molecular sieves are excellent products to separate specifically a number of different gaseous compounds in biogas. Thereby the molecules are usually loosely adsorbed in the cavities of the carbon sieve but not irreversibly bound. The selectivity of adsorption is achieved by different mesh sizes and/or application of different gas pressures.
When the pressure is released the compounds extracted from the biogas are desorbed. The process is therefore often called “pressure swing adsorption” (PSA). To enrich methane from biogas the molecular sieve is applied which is produced from coke rich in pores in the micrometer range. The pores are then further reduced by cracking of the hydrocarbons. In order to reduce the energy consumption for gas compression, a series of vessels are linked together.
The gas pressure released from one vessel is subsequently used by the others. Usually four vessels in a row are used filled with molecular sieve which removes at the same time CO2 and water vapour.
There are two basic systems of biogas purification with membranes: a high pressure gas separation with gas phases on both sides of the membrane, and a low-pressure gas liquid absorption separation where a liquid absorbs the molecules diffusing through the membrane.
- High pressure gas separation
Pressurized gas (36 bar) is first cleaned over for example an activated carbon bed to remove (halogenated) hydrocarbons and hydrogen sulphide from the raw gas as well as oil vapour from the compressors. The carbon bed is followed by a particle filter and a heater. The raw gas is upgraded in 3 stages to a clean gas with 96 % methane or more.
The waste gas from the first two stages is recycled and the methane can be recovered. The waste gas from stage 3 (and in part of stage 2) is flared or used in a steam boiler as it still contains 10 to 20 % methane.
- Gas-liquid absorption membranes
Gas-liquid absorption using membranes is a separation technique which was developed for biogas upgrading in the recent past. The essential element is a micro-porous hydrophobic membrane separating the gaseous from the liquid phase. The molecules from the gas stream, flowing in one direction, which are able to diffuse through the membrane will be absorbed on the other side by the liquid flowing in counter current.
The absorption membranes work at approx. atmospheric pressure (1 bar) which allows low-cost construction. The removal of gaseous components is very efficient. At a temperature of 25 to 35°C the H2S concentration in the raw gas of 2 % is reduced to less than 250 ppm.