upgrading techniques
Final report
J. de Hullu
J.I.W. Maassen
P.A. van Meel
S. Shazad
J.M.P. Vaessen
Financial Feasibility
Table 1 shows that high pressure water scrubbing seems to be the cheap-
est technique to upgrade biogas. Also this technique gives quite high yield
and purity. Cryogenics is the most expensive way of upgrading biogas but it
gives the highest possible yield.
Ease of operation
The operation of the pressure swing adsorption and chemical absorption
process is quite simple. However, the plant needs to shut down several times
per year because the catalyst has to be replaced. Membrane separation and
high pressure water scrubbing are the simplest processes to operate because
they do not need special chemicals or equipment to run. Cryogenics is diffi-
cult to operate because it works on high pressure and really low temperatures
and therefore need good checking of the insulation. But for scaling up cryo-
genics seems to be the most suitable technique.
Conclusion
It can be concluded that high pressure water scrubbing is performing
the best. With the low cost price, high purity and yield it is a promising
upgrading technique. Though one waste stream needs treatment, it is a
continuous process which operates almost on it self.
Preface
Project description
DMT has developed a biogas upgrading technology based on high pressure
water scrubbing. To get a leading position in the market, it is of most
importance to know the advantages and disadvantages of all the different
processes available for upgrading biogas and their cost.
1
A literature study was conducted to create a clear overview of the present
upgrading techniques allowing for an objective comparison. The comparison
of the different options was focused on:
• chemical absorption
• cryogenic separation
• membrane separation
2
Contents
1 Introduction to Biogas 4
2 Upgrading techniques 8
2.1 Chemical absorption . . . . . . . . . . . . . . . . . . . . . . . 8
2.2 High pressure water scrubbing . . . . . . . . . . . . . . . . . . 15
2.3 Pressure swing adsorption . . . . . . . . . . . . . . . . . . . . 20
2.4 Cryogenic separation . . . . . . . . . . . . . . . . . . . . . . . 23
2.5 Membrane separation . . . . . . . . . . . . . . . . . . . . . . . 28
3 Comparison 32
4 Conclusions 35
Acknowledgement 37
Bibliography 38
B Cryogenic equipment 44
C CO2 footprint 46
3
Chapter 1
Introduction to Biogas
The current use of fossil fuels is rapidly depleting the natural reserves. The
natural formation of coal and oil however, is a very slow process which takes
ages. Therefore, a lot of research effort is put into finding renewable fuels
nowadays to replace fossil fuels. Renewable fuels are in balance with the
environment and contribute to a far lesser extent to the greenhouse effect.
Biogas is a renewable fuel, an energy source that can be applied in many
different settings. It is defined as a combustible gas mixture produced by the
anaerobic fermentation of biomass by bacteria and takes only a relatively
short time to form. In nature, the fermentation process occurs in places
where biological material is fermented in an oxygen deprived environment
such as swamps and waterbeds. The two main sources of biogas from human
activities are domestic garbage landfills and fermentation of manure and raw
sewage. The advantage of processing these waste products anaerobically,
compared to aerobically, is the larger decrease in volume of waste product.
For this reason, the industry nowadays prefers anaerobic fermentation to
process waste streams.
Biogas mainly consists of combustible methane (CH4 ) and non-combustible
carbon dioxide (CO2 ). Besides CH4 and CO2 , biogas also contains small
amounts of hydrogen sulphide (H2 S) and some other pollutants. The com-
position of biogas strongly depends on its source. Table 1.1 [1] shows the
composition of biogas from various sources. It can be seen that biogas from
a garbage landfill also contains some nitrogen (N2 ).
CH4 combusts very cleanly with hardly any soot particles or other pol-
lutants, making it a clean fuel. But CO2 , the non-combustible part of the
biogas, lowers the calorific value of the biogas. Biogas containing 60% CH4
has a calorific value of 21.5 MJ/N m3 while pure CH4 has a calorific value of
35.8 MJ/N m3 .
4
Table 1.1: Overview of compositions of biogas from different sources
Component Biogas factory Sewer factory Garbage landfill
CH4 (%) 60-70 55-65 45-55
CO2 (%) 30-40 35-45 30-40
N2 (%) <1 <1 5-15
H2 S (ppm) 10-2000 10-40 50-300
5
Table 1.2: Average compositions of gas used in the commercial gas grid in The Nether-
lands and Canada
Table 1.3: Requirements for injection of biogas into the gas grid
Component Requirement
CO2 < 8 vol %
Water dewpoint < -10◦ C
Oxygen < 0.5 vol %
H2 S < 5 mg/N m3
6
calorific value of the biogas should be at least the value of low calorific gas.
Furthermore, there may be no water or heavier alkanes than propane in the
biogas because it will form condensate at such a high pressure.
Removing CO2 and H2 S from the biogas is not easy. However, the up-
grading technology is rapidly evolving, bringing biogas as a reliable energy
source in sight. To produce large amounts of upgraded biogas, it is necessary
to examine different upgrading methods to see which method might be im-
plemented in the industry. Calculating the so called CO2 footprint of each
technique is valuable to determine the durability [3] [4].
7
Chapter 2
Upgrading techniques
In this chapter, the five investigated upgrading techniques are explained. For
each technique, a short description including a process flow diagram (PFD)
is given and the distinctive advantages and disadvantages of each technique
are discussed. The environmental impact of the upgrading processes is an
important factor to compare the different techniques, so this is discussed for
each technique. In order to compare the different techniques, the cost price
of the produced upgraded gas must also be taken into account. The cost
price per N m3 biogas are calculated using the following formula, in which
the interest rate on the investment is taken to be 6%:
investment
depreciation period
+ investment · interest rate + annual cost
P rice per N m3 =
N m3 produced upgraded gas per year
(2.1)
For each technique the input flow is taken to be 250 N m3 /h containing
60 % of CH4 . The output is calculated as follows:
8
2.1.1 Chemical absorption of CO2
Multiple theories exist about the removal of CO2 in gas streams. However,
these theories are often contradictive. In the following text, CO2 absorption
using aqueous amino acid salt solutions will be discussed.
Cooler
Biogas out
CO2
Absorption
column
Regeneration
column
Heat
exchanger
Gas
stream in
An amino acid dissolved in water exists as a zwitter ion. A zwitter ion can
have a positive and a negative charge depending on the pH of the solution.
The amino group has to be deprotonated before it reacts with CO2 . This
deprotonation is mostly done by addition of an equimolar amount of base,
according to the following mechanism [5]:
HOOC − R1 − N H3+
OOC − R2 − N H3+
OOC − R3 − N H2 (2.3)
2 RN H2 + CO2
RN HCOO− + RN H3+ (2.4)
9
CO2 + OH −
HCO3− (2.5)
RN H3+
RN H2 + H + (2.6)
H2 O
H + + OH − (2.7)
In reaction 2.4, the reaction of CO2 with an amino acid can be seen. The
contribution of reaction 2.5 to the conversion of CO2 is not significant, while
not much OH − ions are present in the solution because the pH is very low.
Since the OH − ions are in equilibrium with the amine molecules, reactions
2.6 and 2.7 have to be taken into account.
This study also discusses the Membrane Gas Absorption (MGA) inves-
tigated by TNO [6]. Research has been done by TNO at the membrane
absorption technique. According to TNO, this is a technique which makes
use of porous, water-repelling membranes for transport of components. Cur-
rently, new absorption liquids, called CORAL, are developed, which show a
stable operation with cheap olefin membranes. According to P.S. Kumar et
al. the MGA technique is economically not very attractive in comparison to
conventional absorption processes, because of the limited availability of the
fibres. The process flow diagram of the CO2 absorption process is shown in
figure 2.1.
H2 S(g) + H2 O
H2 S(aq) (2.9)
10
H2 S(aq)
H + + HS − (2.10)
HS −
H + + S 2− (2.11)
S 2− + 2F e3+
S + 2F e2+ (2.12)
By means of oxygenation the aqueous iron-chelated solution will be re-
generated. This oxygenation is followed by conversion of the pseudo-catalyst
into its active form F e3+ . This mechanism is shown in the following equa-
tions:
1 1
O2 (g) + H2 O(l) → O2 (aq) (2.13)
2 2
1
O2 (aq) + 2F e2+ → 2F e3+ + 2OH − (2.14)
2
In this mechanism, several chelate agents can be used for the specific
proposal of the overall reaction, with the EDT A being the most used common
chelate [10]. In this process, the sulphur produced can be removed easily from
the slurry by sedimentation or filtration operations. Next to that, the whole
process can be carried out at ambient temperature.
11
Figure 2.2 shows an overview of the units that are used to remove the
H2 S from the biogas stream. The complete system consists of an absorber
column, a particle separator or filter, and a regeneration column. Under
continuous operating conditions, the biogas is introduced as small bubbles
at the bottom of the absorber of the column. These bubbles pass through
the F e/EDT A solution flowing downwards to the particle separator. In
the absorber column the H2 S will be absorbed and transformed into S. The
mechanism of this transformation can be seen in the equations in the former
section. In the particle separator, the small particles of S that have formed
are separated from the product stream. After this separation, the outgoing
product stream is regenerated from F e2+ /EDT A into F e3+ /EDT A in a
bubbling air column. The last step in this purification is washing the treated
biogas with water in a packed column to remove residual traces of H2 S.
The advantages of this absorption process are the almost complete re-
moval of H2 S from the biogas. The removed H2 S is also converted into its
elemental form, so it can be sold to other companies. A big disadvantage
is that after the absorption process a scrubber is still needed to remove the
CO2 . It is not possible with this absorption process to remove the CO2 .
Waste streams
Chemical absorption of CO2
The only process stream next to biogas needed in the absorption process is
a liquid water phase in which amines are dissolved. As can be seen in figure
2.1 the biogas flows through a column filled with the amine solution. In this
column, the CO2 is split from the biogas and the biogas leaves the absorption
column. The amine solution including the captured CO2 leaves the column
and will be generated in the generation column. During this process, the
CO2 is split off and is emitted in the atmosphere as a waste stream. The
amine solution will be regenerated and flows back into the column to capture
CO2 again. This solution must be replaced a few times a year and then it
becomes a waste stream too. This solution can be separated into a water
phase and the amines using a membrane. The clean water phase can then
be purged to a river. The only real waste streams are the CO2 stream and
the amines.
Chemical absorption of H2 S
For the H2 S absorption process only the removal of H2 S is taken into account.
In figure 2.2 a scrubber is also shown, but since this process is discussed in
12
another part of the report, we will focus only on the H2 S removal. Figure
2.2 shows the process flow diagram. The biogas stream can be seen and
in the regeneration part also some other streams are added to the process.
The biogas flows through the absorption column and the H2 S is captured
in the liquid phase. The liquid phase consists of water in which F e/EDT A
is dissolved. The biogas leaves the column containing almost no H2 S. The
F e/EDT A solution flows to the regeneration part in which the sulphur is
separated from the solution. After this step, the F e is regenerated from
F e2+ to F e3+ . This aqueous solution is again used in the absorber column
to capture H2 S. The separated elemental sulphur is collected and because
it is pure it can be sold to other companies. However, the amount is small
and to sell a reasonable amount would take quite a long time to collect.
Because of these circumstances, the sulphur is mostly treated as a waste
stream and has to be put away as chemical waste. Another waste stream is
the F e/EDT A solution. This solution has to be replaced a few times a year.
The solution can be filtered using a membrane, to separate the water phase
and the F e/EDT A complexes. These components are another waste stream
of the absorption process and need to be disposed of as chemical waste.
The purity of the obtained biogas is approximately 98%. In both processes
the yield for CH4 is 90%. The CH4 waste stream is best handled by sending
the stream to a flare. Burning CH4 is better for the atmosphere than emitting
the gas. Looking at the two absorption processes the absorption of CO2 seems
to have less waste streams than the absorption of H2 S, at least less harmful
waste streams.
13
Investment costs
Absorber column2 € 125,000
Additional costs6 € 100,000
Pump 3 € 5,000
Heat exchanger4 € 15,000
Cooler1 € 18,000
Regeneration column1 € 90,000
Running costs
Energy costs6 € 30,000
Catalyst costs5 € 50,000
Operator € 50,000
Maintenance6 € 4,500
Investment costs
Absorber column2 € 125,000
Additional costs6 € 100,000
2 Pumps3 € 10,000
Regeneration column1 € 90,000
Particle separator1 € 100,000
14
Depreciation period of equipment is 10 years.
Running costs
Energy costs6 € 30,000
Catalyst costs5 € 15,000
Operator € 50,000
Maintenance6 € 4,500
When the price of the complete upgrading process, including both CO2
and H2 S absorption, is calculated, we obtain a price of € 0.28 per N m3
upgraded biogas. This price is based on the following values:
1
costs from Aspen Icarus Project Evaluator
2
costs from offer of Rootselaar
3
costs from offer of Grundfoss
4
costs from calculation of Mauri
5
costs from excursion to Cirmac
6
costs from offer of E-kwadraat
15
Figure 2.3: PFD for high pressure water scrubbing
In the flash vessel the pressure is decreased and some traces of CH4 will be
regenerated. In the stripper the washing water is regenerated. CO2 and H2 S
are stripped by air in this vessel. After a drying step, the obtained CH4
purity can reach 98% using this process and yields can achieved up to 94%.
There are two types of water scrubbing [2]:
Regenerative absorption
In regenerative absorption, the washing water is regenerated after wash-
ing the biogas. The main advantage of this technique is that the total
amount of water required is much lower compared to single pass scrub-
bing.
16
requires approximately 50 l/h of water. So single pass scrubbing is practi-
cally impossible in The Netherlands because water is too expensive and the
government will have objections against the usage of such large amounts of
water. Therefore, the main focus will be on regenerative absorption.
When working at high pressure, there are two advantages compared to
working at atmospheric pressure. The main advantage is that the dissolu-
bility increases when the pressure is higher. This results in a lower required
amount of water per amount of biogas. The total amount of water required
will thus be a lot lower. Also, the washing water is oversaturated at atmo-
spheric pressure so regenerating will be a lot faster. The driving force behind
the regenerating process is the concentration difference between the oversat-
urated concentration and the equilibrium concentration. With this being as
high as possible, the speed of the process will be highest.
For the design of a water scrubber it is rather important to know how
much H2 S and CO2 can be dissolved. The increasing dissolubility of H2 S
and CO2 with increasing pressure is described by Henry’s Law:
Pi = H · Cmax (2.15)
Cmax Saturation concentration of the component [mol/m3 ]
H Henry’s coefficient [P a · m3 /mol]
Pi Partial pressure of the component [P a]
According to Dalton’s law, the total pressure is the sum of all partial
pressures. So if the total pressure is increased, the partial pressure increases
by the same factor. This means the saturation concentration rises as well.
However, when higher pressures are reached, the dissolubility of the com-
ponents will no longer linearly increase with the pressure. At higher pressures
the increase of dissolubility becomes lower. Up to a pressure of 20 bars the
dissolubility can be described according to Henry’s law [11]. These calcula-
tions are based on the ideal situation so non idealities should be taken into
account in the design of a scrubber.
Another important factor for the dissolubility of the components in water
is the pH [2]. Furthermore, the pH depends on the amount of H2 S and CO2
that has been dissolved into water. Water becomes more acid when more H2 S
and CO2 are absorbed. When the pH is decreased, CO2 will dissolve less and
the H2 S will dissolve less. At a pH of 1, the dissolubility of H2 S is only half
of the dissolubility at a pH of 7. Therefore, a low pH is not feasible because
the H2 S removal is important; the stripping process becomes more difficult
and acid water damages equipment. Working at a high pH is unfeasible as
well because sulphur and carbonate ions will precipitate. It is best to work
at a pH of 7.
17
The mass transfer of components from the gas phase to the water phase
and vice versa is important to know. When it is known, the dimensions of the
reactor can be calculated. Mass transfer occurs when a high concentration
difference between two phases is realized. The mass transfer can be described
using the double film model. This model is shown in figure 2.4.
When two layers with different concentration profiles intersect, the fol-
lowing equations are valid:
18
back to the absorption column. This regeneration can be done by depressur-
izing or by stripping with air in a similar column. When levels of H2 S are
high it is not recommended to strip with air because the water can become
contaminated with elemental sulfur which causes operational problems. Also
at high levels of H2 S the dissolubility is limited because of decreasing pH.
Waste streams
The water scrubbing process contains two main waste streams. The first
waste stream is the exhaust of air which was used to strip the regenerated
water. This stream mainly consists of air and a high percentage of CO2 but
also contains traces of H2 S. Because H2 S is rather poisonous this stream
needs to be treated. Also the stream contains small amounts of CH4 . Because
CH4 is far more damaging to the environmental than CO2 the CH4 in this
stream should be burned.
The second waste stream is a purge of water. To keep the dissolubility
as high as possible a part of the washed water is purged and replaced with
clean water. In this way the concentration of CO2 and H2 S in the water
stream to the scrubber will remain as low as possible and CO2 and H2 S will
not accumulate. Because most of the CO2 and H2 S will be absorbed in the
gas phase in the stripper the purge stream does not have to be treated.
Running costs
Energy costs € 60,000
Operator € 50,000
19
This cost price is in close accordance to the costs in Tilburg at the biogas
upgrading plant, SMB Stortgas BV. At this upgrading plant the cost price
was approximately € 0.11 to € 0.12 per N m3 .
20
Figure 2.5: The principle of pressure swing adsorption, picture taken from [17]
atmospheric pressure. The gas leaving the vessel during this step contains
significant amounts of CH4 and is recycled to the gas inlet. These significant
amounts of CH4 were trapped within the voids of the adsorbent particles.
Before the adsorption phase starts again, the adsorber vessel is repressurized
stepwise to the final adsorption pressure. After a pressure balance with an
adsorber that has been in adsorption mode before, the final pressure build-up
is achieved with feed gas. A complete cycle is completed in approximately
3-5 minutes [20]. The advantages of the PSA-process are the high CH4 -
enrichment of more than 97%, the low power demand and the low level of
emission. The waste stream of the PSA-plant consists of N2 , O2 , H2 O, H2 S
and CO2 . The main disadvantage is the H2 S-removal step. This is a complex
step in the process, which is necessary.
Waste streams
The PSA-plant has a final product stream, the upgraded biogas, which con-
tains more than 97% CH4 . Next to the product stream, a waste stream is
produced. The waste stream leaves the adsorber vessels at the bottom and
contains all the adsorbed material from the carbon molecular sieves. Also,
some significant amounts of CH4 are found in this waste stream (among other
21
Figure 2.6: PFD for pressure swing adsorption [17]
22
sieve. The choice for this adsorbent material can be explained by the ability of
removing N2 and O2 from the biogas. The lifetime of the adsorbent material
is taken to be 3 to 4 years. Furthermore, there are four adsorber vessels
needed in the plant. Figure 2.6 shows the overall scheme of the PSA-plant.
The compressor, the four adsorber vessels, the vacuum pump and the H2 S-
removal step are included in the cost estimation. Appendix A shows an
alternate way of estimating the cost of a PSA-plant. The equations used, are
found in [18, 19]. In this chapter, the cost estimation is adjusted to the cost
estimations of the other techniques which are investigated.
Investment costs
CO2 adsorber columns (4) 4 € 500,000
Additional costs6 € 70,000
Pumps (2) 3
€ 10,000
Compressors (2) € 100,000
Total investment costs € 680,000
Depreciation period of equipment is 10 years.
Running costs
Energy costs € 33,500
Catalyst costs € 100,000
Operator € 50,000
Maintenance € 3,750
23
at different temperature-pressure domains, it is possible to obtain CH4 from
biogas by cooling and compressing the crude biogas to liquefy CO2 which is
then easily separated from the remaining gas.
Among the existing techniques for biogas upgrading, cryogenic separation
of impurities from biogas is still in the early stages of research and develop-
ment. In order to investigate the feasibility of this technique, in the first
designing steps, the focus has been only on the separation under low tem-
perature and high pressure. When the desired purity of the upgraded gas is
achieved, the designing of the cooling and compressing unit in this technique
can be continued. Finally these two models, for compressing and separat-
ing of biogas, is put together to achieve the final separation model which is
shown in figure 2.9. Figure 2.7 shows this primary model for the cryogenic
separation of biogas. The calculations for this model are based on the crude
inlet biogas with an inlet gas flow of 250 N m3 /h. The inlet gas is assumed
to be dried, under atmospheric pressure and has an ambient temperature.
The composition of the inlet gas is given in table 2.1.
Distillation Column
The model in figure 2.7 has been created by using the Aspen Plus software
package. In this model, the impurities from crude biogas are separated using
a distillation column which operates at a temperature of -90 ◦ C and a pressure
of 40 bars. The results of the modeling are summarized in table 2.2.
As can be seen in table 2.2 the product stream, upgraded biogas (stream
2), has a CH4 purity of 91%. Again it should be mentioned here that this
purity is based on the model made in Aspen Plus. However, according to [31]
it should be possible to upgrade biogas to a higher purity of CH4 . Another
demand for the upgrading of biogas is the reduction of H2 S quality with a
24
Table 2.1: The average biogas composition assumed for use in the model [21]
Table 2.2: The results of the modeling for the cryogenic separation
Stream 1 2 3
Temperature (◦ C) 25 -91 1.4
Pressure (bar) 1 40 40
Vapor Fraction 1 1 0
Mole Flow (kmol/h) 10.11 6.48 3.63
Mass Flow (kg/h) 263.42 105.63 157.78
Volume Flow (m3 /h) 250 1.26 0.17
Enthalpy (M M kcal/h) -0.44 -0.11 -0.34
Mass Fractions
CH4 0.369 0.91 0.006
CO2 0.591 0.00014 0.98
CO 0.001 0.004 1.91E-09
N2 0.032 0.08 2.29E-08
H2 0.001 0.003 4.23E-15
H2 S 0.004 Trace 0.006
factor 1000 which is achieved as well. Knowing these demands are achieved,
the second step in the process design will be designing of the cooling and
compressing units. Figure 2.8 shows these process units.
In these process units the crude inlet biogas goes through the first heat
exchanger in which it is cooled down to -70 ◦ C. This heat exchanger uses the
product stream as a cooling medium, which has the advantage of preheating
the upgraded biogas before leaving the plant as well as the energy efficiency
benefit of the process. The first cooling step is followed by a cascade of
compressors and heat exchangers which cool the inlet gas down to -10 ◦ C and
compress up to 40 bars before entering the distillation column. To defrost
25
Biogas 1 2 3 4 5
frozen water each heat exchanger needs a parallel heat exchanger. Table 2.3
shows the stream conditions through this process unit.
Table 2.3: Stream conditions through the cooling and compressing process units
Figure 2.9 shows the complete PFD for the cryogenic separation process
Waste streams
The fact cryogenic separation uses no chemicals makes of this separation
an environmental friendly technique. The only waste stream is stream 8
shown in figure 2.9. (The same as stream 3 in figure 2.7) This stream mainly
consists of a high percentage of CO2 but also contains traces of H2 S and
CH4 . Because H2 S is rather poisonous and CH4 is more damaging to the
environment comparing CO2 , this stream needs to be treated.
26
Biogas
25 oC
1 bar
37 % CH4
58 % CO2
5 % other
Recirculation of product stream as cooling agent
Product Waste
91 % CH4 0.6 % CH4
8 % N2 98 % CO2
1% other
Investment costs
Heat Exchanger 1 € 10,300
Heat Exchanger 2 € 26,500
Heat Exchanger 3 € 21,700
Compressor1 € 200,000
Compressor2 € 250,000
Separation train € 400,000
Running costs
Energy costs € 343,000
Operator € 50,000
Maintenance € 4,500
Total running costs € 397,500
27
2.5 Membrane separation
CH4 and CO2 can also be separated using a membrane. Because of the dif-
ference in particle size or affinity, certain molecules pass through a membrane
whilst others do not. The driving force behind this process is a difference in
partial pressure between gases. The properties of this separation technique
are highly dependent on the type of membrane used. Many different mem-
branes are available each with its particular specifications [26]. The general
principle however is basically the same and is explained below on the basis
of a membrane from the Natcogroup [22].
The Natcogroup use membrane gas separation modules which operate on
the basis of selective permeation [22]. The technology takes advantage of
the fact that gases dissolve and diffuse into polymeric materials. If a pres-
sure differential is set up on opposing sides of a polymeric film, a membrane,
transport across the film (permeation) will occur. The rate of permeation
is determined by the product of a solubility coefficient and a diffusion co-
efficient. Very small molecules and highly soluble molecules (such as He,
H2 , CO2 and H2 S), permeate faster than large molecules (such as N2 , C1 ,
C2 and heavier hydrocarbons including CH4 ). When a biogas stream con-
taining CO2 is fed to a membrane, the CO2 will permeate the membrane at
a faster rate than the natural gas components. Thus, the pressurized feed
stream (coming from below in picture 2.10) is separated into a CO2 rich, low
pressure permeate stream on the right hand side and a CO2 -depleted, high
pressure CH4 gas stream.
Any polymeric material will separate gases to some extent. Proper selec-
tion of the polymeric material comprising the membrane is extremely impor-
28
tant. It determines the ultimate performance of the gas separation module.
Membranes made of polymers and copolymers in the form of a flat film or a
hollow fibre have been used for gas separation. Several different membranes
have been found in literature. The Natcogroup use cellulose acetate as a
base membrane material [22]. Cellulose acetate is very inert and stable in
CO2 /hydrocarbon environments. Application of polyimide membranes has
also been found [23]. For this type of membrane a single stage unit is suffi-
cient to achieve 94% enrichment from gas with a common concentration of
CH4 . Using a liquid as a membrane is also possible making it possible to
replace the membrane in situ by circulating the liquid [24].
The permeation of H2 S depends on the choice of membrane. If H2 S
permeates only partly both exit streams contain H2 S. Either the input
stream or the output streams can be cleaned. Since the CO2 rich stream
still contains a relatively high concentration of CH4 ( 10-15%) this stream
is best used in a gas engine to produce electricity or heat. For that, the
H2 S does not have to be removed. This will result in more wear of the
engine but maintaining an engine is cheaper than the removal of H2 S. The
cheapest option therefore is only cleaning the CH4 stream which constitutes
a significantly smaller amount of gas than the input. A membrane which
fully removes the H2 S from the biogas would be a great improvement. The
need for other pre-treatment such as drying or heating is fully dependent
on the membrane used. A higher pressure gives a higher gas flux through
the membrane. However, the maximum pressure is determined again by the
membrane. For this reason, high strength hollow fibre membranes have been
developed.
Overall, the efficiency of the entire process mainly depends on the mem-
brane used. Its selectivity towards the gases having to be separated, mem-
brane flux or permeability, lifetime, operational temperature and humidity
range, maintenance and replacement costs are all factors that determine the
overall performance of such a biogas upgrading technique. It is therefore
difficult to judge this technique in total. Some main characteristics can be
given; it is a proven technology. It has been applied for many years to extract
nitrogen from ambient air. It has also already been used to upgrade biogas;
experimentally [27] as well as commercially. Membranes, especially hollow
fibre membranes, are very compact, light weight and allow for a modular de-
sign making expansion and replacement very easy. However, well maintained
membranes hardly need any maintenance and can last as long as 10 to 15
years. Other equipment such as the compressor and pumps do need mainte-
nance but this is also true for the other techniques. The total energy needs
are very low since the membrane itself is passive. Because the membrane
is passive the entire process is easy to operate and simple to understand.
29
Membranes however can be expensive and also very fragile. Certain solvents
or fine colloidal solids such as graphite can permanently destroy or foul the
membrane.
Waste streams
A major disadvantage of this technique is the low methane yield. The waste
gas still contains CH4 which is highly polluting. Part of it can be fed back
into the inlet or, as mentioned above, the waste gas can be burnt in a gas
engine linked to a generator. Using a multistage setup also increases the
yield. Positive results have been found using an internally staged permeator
[25], depicted in figure 2.11. Electrical costs are low since only a compressor
has to be powered. The generator can power the compressor which results
in an even higher CH4 efficiency. The CO2 stream is then of no further use.
If the waste stream is not burned in an engine it is very polluting since CH4
is far more harmful than just CO2 .
CH4 + CO2
mainly CO2 +
small amount of CH4
mainly CH4 +
small amount of CO2
· Without H2 S removal
· 150 hours of maintenance per year
· Flare recommended (especially during start-up)
30
Output: 130 N m3 /h, 1,002,400 N m3 per year
78% CH4 yield, purity output: 89.5% CH4
Investment costs
Additional costs € 100,000
Pumps (2) € 10,000
Compressor (5-10 bar) € 100,000
Membrane2 € 23,000
Running costs
Energy costs (41 kW h) € 28,000
Operator € 50,000
Maintenance1 € 3,750
1
Estimate E-kwadraat
2
Estimate from Cirmac
31
Chapter 3
Comparison
This chapter will compare the five different techniques which are investigated
for biogas upgrading. The techniques will be compared on a couple of fac-
tors. Of course, every technique has its own advantages and disadvantages,
but there is more than that. The techniques will be compared on the price
per N m3 upgraded biogas; how easy or hard the process runs looking at
maintenance and scale up; and the impact on the environment by examin-
ing the waste streams. The cost estimate is used to calculate the price of
one N m3 of upgraded biogas. Also, there are the costs of investment and
the operating costs. The consideration to be made is the best combination
of advantages and disadvantages, the cost for operating and investment and
finally, the price which has to be paid for the upgraded biogas, the waste
streams and maintenance. The table at the end of this chapter gives an
overview of this comparison. Furthermore, appendix ?? gives the advantages
and disadvantages of each technique in the current opinion of DMT [29].
These are compared to the findings presented in this report.
Finances
Looking at the price of the upgraded biogas, it can be seen that high
pressure water scrubbing is the cheapest. This can be linked to the invest-
ment costs which also are the lowest. Cryogenic separation sticks out of the
list with the highest investment cost and also the cost price is with € 0.44
the highest. While the investment costs of pressure swing absorption are also
quite high, the cost price is the average compared to the other four techniques.
32
streams. But it does not automatically mean that chemical absorption and
high pressure water scrubbing are a bad technique. Not only the amount of
waste streams has to be noticed, also the content of the waste streams have to
be determined. The waste stream produced with pressure swing absorption
and membrane separation both will be led to a gas engine linked to a gener-
ator. This is the best solution, because CH4 is more harmful when emitted
into air compared to burning a waste stream containing CH4 . Chemical ab-
sorption has two real waste streams, namely a stream containing CO2 and
a stream periodically catalyst stream. High pressure water scrubbing has a
waste stream containing CO2 and some traces of H2 S. The last component is
poisonous, which result in the fact that this waste stream needs waste treat-
ment. The second waste stream is a water stream containing CO2 and H2 S.
Because the amount of CO2 and H2 S is rather small, this stream does not
need any treatment. Cryogenic separation has one waste stream containing a
high percentage of CO2 and some traces of H2 S and CH4 . This waste stream
needs treatment. High pressure water scrubbing and membrane separation
are the only two techniques that don’t produce pure CO2 .
Ease of operation
Not each technique requires the same amount of maintenance, materials,
catalyst and operators. Therefore, a distinction between this has to be made.
Looking at chemical absorption, an expensive catalyst is used in order to
absorb CO2 and H2 S. This catalyst has to be changed twice a year, which
leads to a shut down. The same is partly true for pressure swing adsorption.
High pressure water scrubbing however is a very simple process. The only
separation parameter is the pressure of the water scrubber and this can be
easily kept under the desired condition. Because of this easiness, there is
still an operator needed to check if everything goes well, which is there all
the time. Another advantage is the absence of using special chemicals or
a catalyst, which makes that the process can run continuously without a
periodic shut down. Since membrane separation only needs few equipment
and makes no use of chemicals, no operator is needed which is constantly at
the plant. However, in order to check the running process, one operator is
needed. Another consequence is the simple process, which makes it an easy
running process. At last, cryogenic separation is looked at. Because of the
large amount of equipment needed, it is a complex process. Furthermore, the
high pressure and very low temperature makes it a dangerous process, which
has to be controlled. Operators are certainly needed therefore.
33
Table 3.1: An overview in order to compare the different techniques on our criteria, without H2 S removal. Only for PSA, an
H2 S removal step is needed as pre-treatment. For the other processes, H2 S can be removed in advance or afterwards.
High pressure 265,000 110,000 0.13 94 98 · Removes gases and particu- · Limitation of H2 S absorption
water scrubbing late matter due to changing pH
· High purity, good yield · H2 S damages equipment
· Simple technique, no spe- · Requires a lot of water, even
cial chemicals or equipment re- with the regenerative process
quired
· Neutralization of corrosive
gases
Pressure swing 680,000 187,250 0.25 91 98 · More than 97% CH4 enrich- · Additional complex H2 S re-
adsorption ment moval step needed
· Low power demand
· Low level of emissions
· Adsorption of N2 and O2
Cryogenic sepa- 908,500 397,500 0.44 98 91 · Can produce large quantities · A lot of equipment is required
ration with high purity
· Easy scaling up
· No chemicals used in the pro-
cess
Membrane 233,000 81,750 0.12 78 89.5 · Compact and light in weight · Relatively low CH4 yield
separation · Low maintenance · H2 S removal step needed
· Low energy requirements · Membranes can be expensive
· Easy process
Chapter 4
Conclusions
Comparing the five techniques for the upgrading of biogas with the goal of
injecting it into the commercial gas grid is done in the previous section. From
that, it can be concluded that looking only at the cost price, high pressure
water scrubbing is the best option. But there is more than only cost price
to make a process succeed or fail. Therefore, some other criteria are set up.
The waste stream inventory gives another picture. Pressure swing adsorption
and membrane separation are the only two techniques which have only one
waste stream, which can be cleverly used by driving a generator. The other
techniques have waste streams which need some waste treatment, which also
have to be taken into account looking from an environmental and economical
point of view.
Furthermore, the yield and purity is of great importance. The purity of
the upgraded biogas is comparable for most of the techniques, but membrane
separation has the lowest purity of 89.5% CH4 . The other techniques have a
purity of 98% CH4 . The yield of methane achieved with chemical absorption
is the highest with 98%. Pressure swing adsorption, chemical absorption and
cryogenic separation are at average, where membrane separation is the lowest
with 78% CH4 yield. Membranes in series increase the yield, but this results
also in an increase in costs.
Considering the ease of operation of each process, membrane separation
and high pressure water scrubbing are the easiest processes to operate. No
catalysts or chemicals are needed. Cryogenic separation has the problem of
the need to work at very low temperatures and high pressures. Therefore,
it needs to be controlled by an operator and some safety restrictions have
to be set, because of the high possibility of explosion. Chemical absorption
and pressure swing adsorption both need a catalyst in order to upgrade the
biogas. This catalyst has to be changed twice a year which leads to a shut
down.
35
From this all, it can be concluded that high pressure water scrubbing
performs the best. With the low cost price, high purity and yield it is a
promising upgrading technique. Though one waste stream needs treatment,
it is a continuous process which operates almost on it self.
Recommendations
For further investigation we recommend the following subjects:
• The CO2 footprint is mentioned in the report but not calculated. When
mass balances are made the CO2 footprint can also be calculated.
36
Acknowledgement
During our Multi Disciplinary Project we received help from may people.
Without their help we would not have been able to successfully finish this
project. Therefore our gratitude goes out to the following people.
First of all we want to thank Laura, our tutor. We greatly appreciated
Laura’s presence during our weekly meetings. Her input was always insight-
ful. Although she was rather quiet, the things she said were well worth
listening to.
We would like to thank the people at Dirkse Milieutechnology, in particu-
lar Robert Lems, Déborah Felisoni and Pieter-Durk van Jaarsveld for making
this project possible and receiving us at DMT in Joure. We gathered lots
of useful information and had some good fun during our overnight stay in
Joure.
Furthermore we thank René van den Kieboom for making the excursion
to Tilburg possible and thank Maarten van der Heuvel and Olivier Kuijer
for arranging the excursion to Nuenen. Both excursions were a real addition
to our project and gave us a good understanding of the reality of upgrading
biogas.
Also, we would like to thank Jetse Reijenga, our project coordinator, for
always being attentive to our work and his interest in our progress. The
short introduction into building websites was quite helpful and resulted in
an awesome website for our project.
37
Bibliography
[2] Harry Benning, Opwerken van biogas naar aardgas kwaliteit, maart 2005
[5] TNO Environment, Energy and Process Innovation, CO2 -recovery using
membrane gas absorption, brochure
[6] P.S. Kumar, J.A. Hogendoorn, P.H.M. Feron, G.F. Versteegh, New ab-
sorption liquids for the removal of CO2 from dilute gas streams using
membrane contactors, Chem. Eng. 57, 2002, 1639 - 1651
[7] Horikawa, M.S., Rossi, F., Gimenes, M.L., Costa C.M.M., Da Silva,
M.G.C., Chemical absorption of H2 S for biogas purification, Universi-
dade Estaldual de Maringá, 2001
[8] Astarita, G., Gioia, F., Hydrogen sulphide chemical absorption, Chemical
Engineering Science, 1964, vol. 19, pp. 963 - 971
[9] OBrien, M., Catalytic Oxidation of Sulfides in Biogas, Ventilation Air and
Wastewater Streams from Anaerobic Digesters, Proceedings 1991 Food
Industry Environmental Conference, USA, 1991
38
[13] Eneco, http : //mkb.eneco.nl/productene nt arieven/tarieven/
tarieven.asp
[14] WMD, http : //www.wmd.nl/M ijnW M D/T arief N ota/
T arievenGrootverbruik.html
[15] http://www.biotech-ind.co.uk/Methane-RGP-Process.htm, visited at
the 24th of February 2008
[16] O. Jönsson, M. Persson, Biogas as transportation fuel, Swedish Gas Cen-
tre, 2003
[17] Dr. Alfons Schulte-Schulze Berndt, Intelligent Utilization of Biogas -
Upgrading and Adding to the Grid, Jonköping, May 2006
[18] O. Smith, A. Westerberg, The optimal design of pressure swing adsorp-
tion systems, Chemical engineering science, Vol. 45, No. 12, pp. 2967 -
2976, 1991
[19] P. Cruz, J. Santos, F. Magalhães, A. Mendes, Cyclic adsorption sepa-
ration processes : analysis strategy and optimization procedure, Chemical
engineering science, 58 (2003) 3143 - 3158
[20] Information from excursion to Cirmac in Nuenen
[21] http://www.kolumbus.fi/suomen.biokaasukeskus/en/enperus.html, vis-
ited at the 8th of May 2008
[22] Natcogroup, Acid Gas (CO2 ) Separation Systems with Cynara Mem-
branes, July 2007.
[23] M. Harasimowicz, P. Orluk, G. Zakrzewska-Trznadel, A.G. Chmielewski,
Application of polyimide membranes for biogas purification and enrich-
ment, Journal of Hazardous Materials 144 (2007) 698-702.
[24] Asim K. Guha, Sudipto Majumdar and Kamalesh K. Sirkar, A larger-
scale study of gas separation by hollow-fiber-contained liquid membrane
permeator, Journal of Membrane Science 62 (1991) 293-307
[25] K. Li and W.K. Teo, Use of an internally staged permeator in the en-
richment of methane from biogas, Journal of Membrane Science 78 (1993)
181-190
[26] Danial L. Ellig, Joseph B. Althouse and F.P. McCandless, Concentra-
tion of methane from mixtures with carbon dioxide by permeation through
polymeric films, Journal of Membrane Science 6 (1980) 259-263
39
[27] S.A. Stern, B. Krishnakumar, S.G. Charati, W.S. Amato, A.A. Fried-
man, D.J. Fuess, Performance of a bench-scale membrane pilot plant for
the upgrading of biogas in a wastewater treatment plant, Journal of Mem-
brane Science 151 (1998) 63-74
[30] Brochure Biogas CHP, The use of biogas in Tilburg The Netherlands,
2000
[31] Myken A., Jensen J., Dahli A., Final report, Adding Gas from Biomass
to the Gas Grid, Contract No: XVII/4.1030/Z/99-412; Danish Gas Tech-
nology centre a/s, Swedish Gas Center
40
Appendix A
The costs of the pressure swing adsorption depend on which type of adsor-
bent material is used in the columns and the number of units used. The
operational costs are influenced by the operating pressure, which on its turn
is dependent on the adsorbent material. The compressor needed in the be-
ginning in order to compress the incoming biogas is the last element which
contributes to the cost of the whole plant significantly. Compression is ex-
pensive and in order to make it profitable, it is needed to recover the required
pressure. The pressure recovery can be enabled by several pressure valves.
Now, some assumptions are made to be able to make a cost estimation.
The type of adsorbent material used in the PSA is a carbon molecular sieve.
The choice for this adsorbent material can be explained by the ability of
removing N2 and O2 from the biogas. The lifetime of the adsorbent material
is taken to be 3 to 4 years. Furthermore, there are four adsorber vessels
needed in the plant. Figure 2.6 shows the overall scheme of the PSA-plant.
The compressor, the four adsorber vessels, the vacuum pump and the H2 S-
removal step are included in the cost estimation. The several pressure valves
which are required are included in the equations by the modular factor in it.
The costs of the PSA-plant are divided in two parts: operational costs and
capital costs. First, the operational costs will be calculated. The operational
costs depend on the operating pressure, the flow rate, and the dimensions of
the adsorber vessels. Therefore, first those parameters are determined. The
operating pressure of the PSA-plant is 1 bar at the inlet and the product
stream is at 5 bar. The bed length is set at 6 m with a diameter of 1,5 m
assuming cyclic steady state. The inlet flow is assumed to be 250 N m3 /h.
41
The following equation from [19] determines the operational costs:
OC = Qin · W · EC (A.1)
Where:
Where:
P Pressure [P a]
d Bed diameter [m]
l Bed length [m]
In order to calculate the cost of the PSA-plant, also the investment costs
for the H2 S-removal part has to be taken into account, therefore, the costs
used for H2 S-absorption is included which amount to € 516.000,-.
42
The total capital costs are the cost of the bed metal shell summed up with
the costs of the compressor, the costs of the driver of the compressor and the
costs of the H2 S-removing part. The total capital costs become € 1.023.694,-
The total running costs of the PSA can also be calculated by:
CCap
CAnnual = + (1 − tax) · Cop + dr · tax · CCap (A.5)
τpb
The pay back time is set at 3 years, which is equal to 94.608.000 seconds.
The tax rate is assumed to be 0,6 and the depreciation rate 0,125. The total
running costs of the PSA-plant become € 282.616,-.
43
Appendix B
Cryogenic equipment
Compressor 1
Manufacturer: Vilter (http : //www.vilter.com)
Compressor type: oil flooded single screw compressor
Motor power: 180Kw
Price for complete package ready to work: €200,000
Compressor 2
Manufacturer: Vilter (http : //www.vilter.com)
Compressor type: oil flooded single screw compressor
Motor power: 200Kw
Price for complete package ready to work: € 250,000
Heat exchanger 1
Price is calculated by http : //www.matche.com/EquipCost/Exchanger.htm
Heat exchanger type: Condenser, vertical tube
Area: 70 f t2
Internal pressure: 150 psi
Material: Carbon Steel
Heat exchanger 2
Price is calculated by http : //www.matche.com/EquipCost/Exchanger.htm
Heat exchanger type: Condenser, vertical tube
Area: 150 f t2
Internal pressure: 300 psi
Material: Carbon Steel
44
Heat exchanger 3
Price is calculated by http : //www.matche.com/EquipCost/Exchanger.htm
Heat exchanger type: Condenser, vertical tube
Area: 100 f t2
Internal pressure: 150 psi
Material: Carbon Steel
45
Appendix C
CO2 footprint
These steps always have to be followed one by one and boundaries have
to be set. For instance, the carbon footprint can cover all the supply chain
steps from raw material to disposal, but this can be adjusted. Step 3 in the
methodology takes care of that.
46
Figure C.1: The steps used in order to produce the whole supply chain process map,
picture taken from [28]
47
and also to calculate the GreenHouse Gas emissions (GHG emissions) for
each step in the process.
After the five steps, the carbon footprint is ready. It gives insight in the
GHG emissions produced in the process. Then it is necessary to take a critical
look at the environmental performance of your process. When the emissions
are too large or harmful, the carbon footprint can help to design a solution
in order to reduce and control the produced greenhouse gas emissions.
48
Appendix D
49
Figure D.1: The HPWS plant in Tilburg
planned in the middle of our project we had many questions, both about the
technique of biogas upgrading as well as the treating method of the waste
streams and a cost estimation according to this technique. The questions
were extensively answered. Finally we went to the site to have a closer look
at different units of the plant, where the given presentation was coupled to
more detailed information about each separation unit of the plant. We talked
further about the different theoretical features of the process and how they
turn out to behave during operation. The picture shows the plant we visited.
Address
Vloeiveldweg 10
5048 TD Tilburg
Telephone: 013-4556163
50
Appendix E
51
The visit started with a presentation about the plant in Nuenen, in which
we got insight in the processes of pressure swing adsorption and membrane
separation. At that moment we still missed some information about the
cost estimation of a few upgrading processes. Our questions were answered
extensively, which gave us the opportunity to fill the gaps in our theories.
After the presentation, we went outside to take a look at the upgrading
installation. The installation we viewed can be seen in the picture, it is a
vacuum pressure swing adsorption (VPSA) installation. We discussed the
different theoretical features of the process and how these turn out to behave
during operation. Furthermore, we spoke about the waste streams, how they
are kept as low as possible and how they are disposed.
Finally, we walked to the top of a landfill, to have a look at the biogas
wells and to see how a landfill is operated to obtain a large amount biogas
with the right conditions.
Address
Gulberg 7
5674 TE Nuenen
Telephone: 040-839683
52