Biological Cleanup of Biogas

The most valuable component of biogas is methane (CH4) which typically makes up 60%, with the balance being carbon dioxide (CO2) and small percentages of other gases. However, biogas also contain significant amount of hydrogen sulfide (H2S) gas which needs to be stripped off due to its highly corrosive nature. Hydrogen sulfide is oxidized into sulfur dioxide which dissolves as sulfuric acid. Sulphuric acid, even in trace amounts, can make a solution extremely acidic. Extremely acidic electrolytes dissolve metals rapidly and speed up the corrosion process.

The corrosive nature of H2S has the potential to destroy expensive biogas processing equipment. Even if there is no oxygen present, biogas can corrode metal. Hydrogen sulphide can become its own electrolyte and absorb directly onto the metal to form corrosion. If the hydrogen sulphide concentration is very low, the corrosion will be slow but will still occur due to the presence of carbon dioxide.

The obvious solution is the use of a biogas cleanup process whereby contaminants in the raw biogas stream are absorbed or scrubbed. Desulphurization of biogas can be performed by biological as well as chemical methods. Biological treatment of hydrogen sulphide typically involves passing the biogas through biologically active media. These treatments may include open bed soil filters, biofilters, fixed film bioscrubbers, suspended growth bioscrubbers and fluidized bed bioreactors.

Biological Desulphurization

The simplest method of desulphurization is the addition of oxygen or air directly into the digester or in a storage tank serving at the same time as gas holder. Thiobacilli are ubiquitous and thus systems do not require inoculation. They grow on the surface of the digestate, which offers the necessary micro-aerophilic surface and at the same time the necessary nutrients. They form yellow clusters of sulphur. Depending on the temperature, the reaction time, the amount and place of the air added the hydrogen sulphide concentration can be reduced by 95 % to less than 50 ppm.

Most of the sulphide oxidising micro-organisms belong to the family of Thiobacillus. For the microbiological oxidation of sulphide it is essential to add stoichiometric amounts of oxygen to the biogas. Depending on the concentration of hydrogen sulphide this corresponds to 2 to 6 % air in biogas. Measures of safety have to be taken to avoid overdosing of air in case of pump failures.

Biofiltration

Biofiltration is one of the most promising clean technologies for reducing emissions of malodorous gases and other pollutants into the atmosphere. In a biofiltration system, the gas stream is passed through a packed bed on which pollutant-degrading microbes are immobilized as biofilm. A biological filter combines water scrubbing and biological desulfurization. Biogas and the separated digestate meet in a counter-current flow in a filter bed. The biogas is mixed with 4% to 6% air before entry into the filter bed. The filter media offer the required surface area for scrubbing, as well as for the attachment of the desulphurizing microorganisms. Microorganisms in the biofilm convert the absorbed H2S into elemental sulphur by metabolic activity. Oxygen is the key parameter that controls the level of oxidation.

The capital costs for biological treatment of biogas are moderate and operational costs are low. This technology is widely available worldwide. However, it may be noted that the biological system is capable to remove even very high amounts of hydrogen sulphide from the biogas but its adaptability to fluctuating hydrogen sulphide contents is not yet proven.

Biogas Upgradation Methods

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

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.

Pressure swing adsoprtion process for biogas upgradation

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 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.