Biogas Enrichment Methods

Enrichment 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 used commercially 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

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.

Membrane Purification

There are two basic systems of gas 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.

PSA System for Biogas Upgradation

Pressure swing adsoprtion, also known as PSA, is emerging as the most popular biogas upgradation technology in many parts of the world. A typical PSA system is composed of four vessels in series that are filled with adsorbent media which is capable of removing water vapor, CO2, N2 and O2 from the biogas stream.

During operation, each adsorber operates in an alternating cycle of adsorption, regeneration and pressure buildup. Dry biogas enters the system through the bottom of one of the adsorbers during the first phase of the process. When passing through the vessel, CO2, N2 and O2 are adsorbed onto the surface of the media. The gas leaving the top of the adsorber vessel contains more than 97% CH4

The upgrading takes place over 4 phases: pressure build-up, adsorption, depressurization and regeneration. The pressure buildup is achieved by equilibrating pressure with a vessel that is at depressurization stage. Final pressure build up occurs by injecting raw biogas. During adsorption, CO2 and/or N2 and/or O2 are adsorbed by the media and the gas exits as CH4.

Depressurization is performed by equalizing with a second pressurizing vessel, and regeneration is achieved at atmospheric pressure, leaving a gas that contains high concentrations of CH4 to be re-circulated. During the regeneration phase, the bed must be regenerated by desorbing (or purging) the adsorbed gases. Purging is accomplished by reducing the pressure in the bed and back-flushing it with some of the concentrated gas product. The gas pressure released from one vessel is used by the other, thus reducing energy consumption and compressor capital costs.

Special adsorption materials are used as a molecular sieve, preferentially adsorbing the target gas species at high pressure. The adsorbent media is usually zeolites (crystalline polymers), carbon molecular sieves or activated carbon. Aside from their ability to discriminate between different gases, adsorbents for PSA-systems are usually very porous materials chosen because of their large surface areas.