The Purification of Biogas
The Purification of Biogas
The Purification of Biogas
The authors:
Helmut Muche, Harald Zimmermann, Ingenieurbüo für Verfahrenstechnik, Lemgo
ISBN 3-528-02015-6
(introduction...)
0. Introduction
1. Properties of hydrogen sulphide
2. The origins of hydrogen sulphide in biogas plants
3. The effect of hydrogen sulphide on the biogas plant and the gas-utilization
equipment
4. Determination of the hydrogen sulphide content of biogas
5. Methods for removing hydrogen sulphide from biogas
6. Purifying absorbent
7. Requirements on the absorbent
8. The desulphurizing apparatus
9. Operation procedures for gas desulphurization
10. Summary
Appendix
0. Introduction
This review attempts to set out the procedures for removing hydrogen sulphide from biogas.
Hydrogen sulphide is particularly harmful when biogas is used in internal combustion engines.
Its chemical reactions and those of its combustion product - sulphur dioxide, quickly lead to
severe corrosion and wear on engines.
The only practical way of removing the hydrogen sulphide on a small scale is by dry
desulphurization using ferrous substances. Locally available, iron-containing soil is suitable for
use as the purifying agent in Third World countries. This manual contains a detailed description
of criteria for designing the purification chamber. It also presents the basic steps for
manufacturing the purifying agent or absorbent.
The paper is mainly directed at staff in the various regional biogas advisory services. In
particular the colleagues must give assistance in selecting the soils, and sometimes carry out
investigations to identify the composition of the substances. Only an optimally applied
purification agent can ensure a long life for the gas user, particularly engines, and avoid
unnecessary repairs and maintenance on the plant equipment.
Hydrogen sulphide (H2S) is a colourless, very poisonous gas. It is inflammable and forms
explosive mixtures with air (oxygen). H2S has a characteristic smell of "rotten eggs". This
odour is only apparent in a small concentration range (0.05-500 ppm).
H2S is soluble in water forming a weak acid. A combustion product of H2S is SO2. This makes
the exhaust gases very corrosive (sulphuric acid) and contaminates the environment (acid
rain).
Toxicity
Lethal dose
Effect
H2S changes the red blood pigment; the blood turns brown to olive in colour. The transport of
oxygen is hindered. The person suffocates "internally". The symptoms are irritation of the
mucous membranes (including the eyes), nausea, vomiting, difficulty in breathing, cyanosis
(discoloration of the skin), delirium and cramps, then respiratory paralysis and cardiac arrest.
At higher concentrations immediate respiratory paralysis and cardiac arrest are the only
symptoms.
Even if a person survives poisoning, longterm damage to the central nervous system and to the
heart remains.
First aid
Fresh air, artificial respiration; warmth, rest, transportation in an inclined position. There is a
danger of suffocation if the patient is unconscious!
Medical care
Chronic effects
Long-term exposure to very small amounts of H2S can lead to chronic poisoning. Symtoms:
irritation of the mucous membranes, sensitivity to light, bronchitis, headaches, weariness,
circulatory disturbances and loss of weight.
Formation
Amounts
Plant material introduces little H2S into biogas. On the other hand, poultry droppings introduce,
on average, up to 0.5 vol. % H2S, cattle and pig manure about 0.3 vol. % H2S.
Protein-rich waste (e.g. swill, molasses etc.) can produce large amounts of hydrogen sulphide
(up to 3 vol. %). Inorganic sulphates (from salty, stall rinse water or diluting water) also
produce considerable H2S.
Fermentation inhibition
Dissolved H2S is contained in the fermentation slurry. An equilibrium is set up between the
dissolved H2S and the H2S in the gas phase. The dissolved H2S in high concentrations can be
toxic to the bacteria in the slurry. It can inhibit the production of biogas and cause its
composition to alter.
Remedies - put less sulphur-rich material in the plant, dilute with water. In less serious cases
stir vigorously (to drive H2S out of the slurry).
Corrosion by H2S
The presence of H2S gas in biogas makes it corrosive to metal parts. Iron is subject to surface
attack, although not major corrosion. Galvanized parts are similarly subject to surface
corrosion.
The effect on non-ferrous metals in components, such as pressure regulators, gas meters,
valves and mountings, is much more serious. They are very quickly corroded. These materials
also corrode in gas engines (seals and valves).
The combustion product SO2 combines with water vapour and badly corrodes the exhaust side
of burners, gas lamps and engines. Burning biogas in stoves and boilers can also result in
damage to the chimney.
Engines
The acid which is formed corrodes engine parts in the combustion chamber, exhaust system
and in various bearings. This is enhanced by frequent starts, short running times and the
relatively low temperatures when starting up and after cutting off the engine. The water cooling
system also provides the means (water needed to form sulphuric acid) for corrosion.
Service life
Running engines with H2S -containing gas can reduce the service time to the first general
overhaul by about 10-15%.
The suphur content of biogas used in gas engines shortens the time between oil changes. SO2
from combustion and water vapour both dissolve in the lubricating oil. The oil becomes acidic
and its properties change. It loses its ability to lubricate and sometimes corrodes metal
components. Under continuous operating conditions the interval between oil changes is reduced
to 200 - 250 hours.
Cooking stoves
If biogas is burned for cooking and lighting in poorly ventilated rooms' the occupants
The H2S content of the purified gas can be measured to check the effectivity of the
desulphurization process.
Laboratory method
In the laboratory the H2S content of gases is usually measured iodometrically using cadmium
acetate. However, the necessary techniques are too involved for an application here.
Another simple method for detecting H2S is with an alcoholic solution of iodine, such as often
available in first aid kits. A small amount of biogas is carefully introduced into the iodine
solution. If H2S is present the reddish brown solution will decolour. The formation of elementary
sulphur causes a milky turbidity.
The test-tube method is a very exact and simple method of determining the H2S concentration
in biogas. Suitable tubes are available for measuring the concentration in both raw and purified
gas. The gas detector apparatus (ca. 450,- DM) and the individual test tubes (ca. 5,- DM each)
are relatively expensive. Also, the test tubes can only be preserved for a limited time. This
method is only expedient in the regional biogas extension service or similar advisory services.
This apparatus could then be used to provide empirical field values for individual plants. The
intervals for recharging the purifying agent can then be laid down.
As yet there is no simple, cheap, test method available. For this reason a close control of the
desulphurization plant is strongly recommended.
General
Of the many processes traditionally and presently employed, that have been used for large-
scale desulphurization of technical gases, only the so-called "dry" process is suitable on a
smaller scale for biogas plants. They are acceptable from the point of view of technical
complexity and maintenance and the degree of purification is satisfactory.
The oldest process is the desulphurization of gases with quick lime, slaked lime in solid form or
with slaked lime in liquid form. The process using quick or slaked lime has not been applied on
a large scale for a long time. The large amounts of odourous residue that are produced cannot
be satisfactorily disposed of. The handling of large amounts of dissolved or suspended slaked
lime requires elaborate equipment.
Large concentrations of CO2 which are present in biogas make the satisfactory removal of H2S
difficult. The CO2 also reacts with the quick and slaked lime and uses it up quickly. The
Ca(HCO3)2 formed reacts with Ca(SH)2 which is formed by the reaction of H2S with Ca(OH)2
thus resulting in the reoccurance of H2S. However, a large scale biogas plant in Germany with
the cogeneration of heat and power has recently been constructed using a lime purifier. The
results of long term tests are not yet available.
In as far as enough lump, quick lime is available in the countries concerned, this process could
be considered for desulphurization. The apparatus for utilizing quick lime corresponds in
construction and function to that used for the desulphurization with iron-containing substances.
Ferrous materials
Ferrous materials in the form of natural soils or certain iron ores are often employed to remove
H2S.
Principle
The ferrous material is placed in a closed, gas tight container (of steel, brickwork or concrete).
The gas to be purified flows through the ferrous absorbing agent from the bottom and leaves
the container at the top, freed from H2S.
Chemistry
The absorbing material must contain iron in the form of oxides, hydrated oxides or hydroxides.
These react as follows:
This process terminates, of course, after some time. The greater part of the iron is then
present as a sulphide.
Regeneration
However, by treating the sulphidized absorbent with atmospheric oxygen, the iron can be
returned to the active oxide form required for the purification of the gas:
The used absorbent can, therefore, be "regenerated". This regeneration cannot be repeated
indefinitely. After a certain time the absorbent becomes coated with elementary sulphur and its
pores become clogged. Purifying absorbents in gasworks (coke plants) acquire a sulphur
content of up to 25% of their original weight, i.e. 40% sulphur by dry weight.
Process techniques
Without regeneration
The purification chamber consists of a box or drum. The absorbent is placed inside it on
several, intermediate trays (sieve floors) to ensure that the depth of the absorbent is not more
than 20-30 cm. Otherwise the absorbent would easily press together causing an increase in the
resistance to the gas flow.
The biogas is fed in at the bottom of the box, flows through the absorbent and leaves the
purification chamber at the top, freed from H2S. When the absorbent becomes loaded with iron
sulphides, the gas leaving the chamber contains increasingly more H2S. The chamber is then
opened at the top and the trays with the spent absorbent are removed. Then fresh absorbent is
placed on the trays.
After the air in the purification chamber has again been displaced with biogas, the gas
connection to the user is re-opened.
The spent absorbent is disposed of as described under the heading "Disposal of spent
absorbent".
With regeneration
The spent, sulphide containing absorbent can also be regenerated by exposing it to oxygen.
This can either be done by taking the used absorbent out of the chamber and exposing it to the
air, or inside the purification chamber by simply sucking ambient air through it.
Since regeneration inside the chamber requires precautions against the formation of unwanted
and dangerous air-gas mixtures and would require powerful fans, regeneration outside the
chamber is usually preferred. The absorbent that is to be regenerated, is spread out on the
ground in as thin a layer as possible. From time to time it is turned over with a shovel. After a
few days it is ready for use again.
This regeneration process can be repeated up to ten times, after which the absorbent is finally
spent.
Simultaneous regeneration and loading of the absorbent is a special case. Here a certain, small
amount of air is added to the biogas. Then sulphide formation and regeneration occur at the
same time and place. As such, the absorbent acts effectively as a catalyst.
Expensive gas-measuring and mixing equipment is required for this process, however, so that
it is not suitable for small biogas plants.
6. Purifying absorbent
General
The industrial absorbents in Europe are native ores or synthetic materials containing iron
hydroxide or hydrated iron oxides. They are employed under such names as "H-Masse", "Lux-
Masse", "Wasserwerks-Masse" and "Raseneisenerz".
Iron content
The iron content calculated as the oxide is decisive and should be at least 40-50% by weight. If
possible the proportion of "active iron" should be more than 70% of the total iron. "Active iron"
is hydrated iron oxide having a particular crystal modification, for instance, alpha-FeOOH and
beta-FeOOH. Certain industrial, iron-containing substances such as iron pyrites and slags etc.,
do not react with H2S even though they have a similar chemical composition. They are
"inactive". Under certain conditions they can be activated by grinding or other mechanical
processing. This partially destroys the crystal structure.
Natural materials
Some naturally occurring, ferruginous soils are suitable for use as absorbents. Those ores or
soils containing large concentrations of hydrated ferric oxides (Fe2O3H2O or FeO(OH)) are
suitable. Such ores are known as brown ironstone. There are various subtypes:
Deposits
Laterite soils occur widely in tropical and subtropical areas. The iron content varies according to
location: some of these laterite deposits are large enough to be mined for the production of
iron.
Since laterite consists mainly of goethite, it is probably suitable for use as an absorbent. It is,
of course, necessary to break or grind the material mechanically to achieve the right particle
size. Since areas with laterite soils are usually cultivated for intensive crop production, i.e. the
basis exists for a biogas plant, this soil appears likely for the purification agent.
The "terra rosa" found in the Mediterranean region is probably also suitable. It contains 10% of
iron, again in the form of goethite.
Activation by regeneration
Some absorbents are less efficient when used for the first time. After they have been
regenerated once the purification effect can be improved. The chemical processes involved
have activated the material.
The absorbents must fulfil certain requirements in order to show a satisfactory, purifying
action.
Alongside the requirements already mentioned concerning the iron content and the chemical
composition, the following are important:
Bulk density
The absorbent must not be too "dense", that is it should possess a certain empty or pore
volume. If the absorbent is too fine, the gas flow will be hindered. The resistance pressure in
the layers and, thus, in the chamber will be too great. In extreme cases the purification
chamber can become blocked.
Grinding, stamping
The absorbent material will normally be found in the form of soil or as lumps which should be
broken up and ground. Stamping with an appropriate tool is a suitable technique.
Comminution increases the surface area (important for the chemical reaction) and secondly,
the crystal structure is improved.
Filler
To obtain the desired porosity, a filler is mixed into the ferrous material. Organic fillers are
suitable. They loosen the texture of the absorbent and bind a certain amount of water into it.
The addition of water and the filler should transform the original powdery, ferrous material into
a friable, crumbly mass. It should not smear if rubbed in the hand, but should also not
pulverize for lack of water.
Bulk density
The bulk density, which is a measure of the porosity, should be 0.7 - 0.8 kg/litre.
The bulk density can be measured by taking a tin can, for example, with a known volume,
filling it loosely with absorbent and weighing it. The absorbent should not be packed down or
pressed - but exactly as it is in the purification chamber.
Particle size
pH value
The finished absorbent should have a pH of at least 5. A slight alkalinity is better. If the natural
soil is acidic due to humic acid or the filler is acidic (peat especially), then the absorbent can be
neutralized by the addition of alkaline material.
The pH value can be adjusted with soda or potash. About 2 to 4% is added to the absorbent.
As a substitute alkaline wood or plant ash could also be used.
This treatment, however, is not expected to be as effective as guaranteeing the optimal particle
size and porosity.
Preparation of the absorbent
8. The desulphurizing apparatus
The absorbent described above must be brought into immediate contact with the gas. This
takes place in closed purification chambers. They can be made of steel, gas-tight brickwork or
concrete.
The area perpendicular to the gas-flow or cross section of the chamber is important. If it is too
small, the gas will flow too quickly through the absorbent and the contact time is too short. If
the gas flow is too fast channels will open in the absorbent. The gas then flows through these
channels and is not properly purified.
The volume (if the cross section is fixed then the height) of the chamber is also important. The
chamber must contain enough absorbent for the gas to be in contact with the absorbent over a
sufficient distance. Apart from this the purification chamber must be large enough so that it
does not constantly need to be refilled.
Dimensioning method
A method for calculating the required size of purification chambers is included at the end of this
manual.
Intermediate trays
The purification chamber contains several intermediate trays. A layer of absorbent cat 20-30
cm thick is placed on each tray. This avoids compacting of the absorbent under its own weight.
The intermediate tray floors are permeable to the biogas. They are made from perforated steel
sheet or wooden slats. Wickerwork can also be used.
The individual, intermediate trays do not rest upon the absorbent in the tray below, but are
supported by small spacers attached to the tray underneath. The layers of absorbent that lie
between should not be compacted.
Inserting absorbent
The absorbent should be placed on the trays in such a way that it is not compressed or packed
down. It should be piled up higher at the chamber walls to avoid the preferable gas penetration
at this position.
The chamber cover should be designed to give access to the whole chamber cross section. This
allows the removal of the intermediate trays from the chamber.
The cover must be sealed with the chamber. A rubber seal made from foam rubber' old bicycle
inner tubes or a water hose would be suitable.
Fixing
Control valves
Control valves are installed in the feed and exit pipes of the purification chamber. These are
used to disconnect the chamber from the gas flow while the absorbent is being exchanged.
Scavenging vent
In addition, a scavenging vent is installed. It is used for flushing air out of the chamber with
new biogas after exchanging the absorbent and sealing the chamber.
When scavenging. the chamber there is a danger of fire and explosion, due to the gas
emerging from the scavenging vent. For this reason the vent exit should be installed high up
and away from buildings. Open flames and smoking must be prohibited during all work on the
purification chamber.
When scavenging is completed, that is, when two or three times the volume of the chamber
has been vented, the valve to the user can be re-opened.
The H2S content of the gas can also be checked via the scavenging vent even during plant
operation (see Section 5).
Desulphurization chamber for biogas
Cylindrical purification chamber
Rectangular purification chamber
Construction of intermediate trays, cross section; The intermediate trays can be made from
9. Operation procedures for gas desulphurization
Filling
Remove the cover of the purification chamber. Put in the bottom tray, which has spacers
attached both below and above. Spread a layer of absorbent 20 - 30 cm thick over it. The
absorbent at the edge of the tray is ´'piled up" against the wall of the chamber.
The second, intermediate tray is then placed on the spacers of the bottom one and covered
with absorbent. Then the rest of the intermediate trays, which are covered in turn with
absorbent, are placed in position.
Sealing
Put the cover on the purification chamber together with the seal and screw it down tight.
Scavenging
Open both the feed valve in front of the chamber and the scavenging vent valve. Leave the
control valve to the user closed. Let a volume of gas equivalent to three times the chamber
volume escape from the scavenging vent (caution danger of fire and explosion!). Then close
the scavenging vent and open the valve to the biogas user.
When the H2S concentration of the purified biogas begins to rise, the absorbent should be
exchanged. See Section 5 for the determination of the H2S of the gas.
Close the control valves (feed and user valves) in front of and behind the purification chamber.
Remove the cover of the chamber. Caution - danger of fire and explosion!
Remove the absorbent layer after layer from the chamber. In some cases the individual
intermediate trays can be removed together with the entire layer of absorbent. Check the trays
for damage and, if necessary, repair or replace them. Then the purification chamber can be
refilled with fresh absorbent.
The sulphur-loaded absorbent can either be regenerated by exposure to the air (oxidation) or
be discarded if there is an ample supply. See the next section for details.
Regeneration
The absorbent is regenerated by spreading it on the ground in a thin layer and turning it over
periodically. It is oxidized again within a few days and can be re-used.
After it has been utilized and regenerated several times the absorbent finally becomes inactive
and must be discarded. Spent material highly concentrated with powdered sulphur reacts under
certain conditions with the oxygen in the air, to form sulphur dioxide - SO2 - which irritates
breathing passages and the eyes, as well as being harmful to the environment.
Self-ignition
It is only seldom that the heat of reaction is sufficient to cause spontaneous combustion. The
spent absorbent should however be disposed of in a way to avoid these problems.
Discarded absorbent should thus be placed in pits and immediately covered with earth. When
this is done the soil bacteria transform the sulphur and sulphides to relatively harmless
sulphates.
It might also be possible to mix the used absorbent with the digested sludge. In this way the
sulphur, which had been removed, could be fed back through the soil to the plants, thus
completing the natural cycle. A decision can only be made after tests under local conditions.
Degree of desulphurization
Since the desulphurization capacity drops with continued use, the efficiency is not constant
during the service life of a charge of absorbent. As it becomes loaded with sulphur, that is as
the sulphur concentration increases, the H2S content of the purified gas also increases. Nearly
complete desulphurization can only be achieved when the absorbent is regularly exchanged and
then discarded. The absorbent is not completely utilized with this procedure and the time
interval between refillings is considerably shortened.
Another way of producing a very low H2S concentration is to use at least two purification
chambers in series, that is one after the other.
The first serves as a coarse purification chamber while the second serves as a fine filler
chamber. Even when the first chamber allows considerable amounts of H2S to pass through,
the second is capable of reliably binding the remainder. The resulting purified biogas is almost
completely free from sulphur.
The absorbent is almost completely utilized. As soon as the first chamber is unable to remove
H2S, its absorbent is exchanged. This chamber is now used as the fine filtering chamber. The
second chamber which was the fine chamber is now used as the first, coarse purification
chamber. That is, the order of the gas flow has been reversed.
The temperature of the gas in the purification chamber should be held as constant as possible
to prevent the absorbent from drying out or becoming moist. If necessary the purification
chamber should be insulated. The chemical reactions in the purification process operate best at
temperatures between 15-25 °C. A higher temperature is better than too low a temperature.
Regeneration of the spent absorbent (1)
Regeneration of the spent absorbent (2)
Starting up the chamber after refilling with regenerated absorbent (1)
Starting up the chamber after refilling with regenerated absorbent (2)
10. Summary
Hydrogen sulphide is a natural component of biogas. Its concentration depends on the sulphur
content of the raw material being digested and lies in the range 1,500 ppm 5,000 ppm or 0,15-
0.5 vol. % or 2.1-7 g H2S/m³. Hydrogen sulphide is responsible for corrosion of various parts of
the plant equipment.
The use of biogas in an internal combustion engine causes uncontrollable corrosion problems.
Engine components are very susceptible to corrosion by H2S and its reaction product SO2.
The experience of various manufacturers and users, as well as the (older) literature indicate
that with the sulphur concentrations mentioned, the service life of the engines can be reduced
by up to 15% of their normal value. Not only are the resulting repair and maintenance costs
increased but also the costs for service materials such as spark plugs and lubricating oils. Even
with special oils the oil change interval drops up to one-fifth of that under normal conditions.
The oil becomes acidic from sulphur dioxide and thus loses its lubricating properties.
Desulphurizing biogas with acceptable investment and operating costs is only possible
employing the dry desulphurization method. Iron-containing materials of specified compositions
are utilized as absorbing agents for H2S. Alongside the traditional, commercially available
absorbents, certain substitutes can be used. Various tropical and subtropical soils contain
sufficient iron in a suitable form. They must be prepared, in order to obtain the proper purifying
characteristics. The material must be loose, porous, moist and granular.
The raw soil has to be ground and mixed with a filler and water to obtain a homogeneous
texture. The finished absorbent is placed on gas-permeable trays in a purification chamber. The
raw biogas is fed in at the bottom and the desulphurized or partially desulphurized gas is
extracted from the upper part of the chamber.
Eventually the absorbing agent is saturated with sulphur and can be regenerated either inside
the chamber or outside through natural ventilation with air (oxygen). The absorbent material
can, therefore, be re-used several times.
Using two or more purification chambers connected in series ensures a continual production of
purified gas and allows a good capacity utilization.
The spent absorbent can be disposed of safely by burying it. Various factors must be
considered when dimensioning the purification chambers. A certain maximum flowspeed should
not be exceeded The gas volume to be purified per unit time determines the cross section of
the purification chamber. The chamber volume and, hence, the amount of absorbent determine
the operating time for the purification process up to regeneration or exhange of the absorbent.
Figure
Figure
Figure
Figure