Comparing different biogas

upgrading techniques
Interim report

J. de Hullu
J.I.W. Maassen
P.A. van Meel
S. Shazad
J.M.P. Vaessen

L. Bini, M.Sc. (tutor)

dr. ir. J.C. Reijenga (coordinator)

Eindhoven University of Technology, April 3, 2008

 Abstract
This interim report is the result of a multidisciplinary project at the Eind-
hoven University of Technology commissioned by Dirkse Milieutechniek BV.
The goal of the project was to research and compare the currently available
techniques to upgrade biogas. Upgrading of biogas comprises the removal of
CO2 , H2 S and other possible pollutants from biogas. CO2 removal increases
the concentration of CH4 which gives the biogas a higher calorific value al-
lowing for injection in the gas grid. H2 S has to be removed because of its
corrosiveness.

Five techniques have been investigated. Chemical absorption of H2 S

into iron-chelated solutions offers a highly efficient removal of H2 S from a
gaseous biogas stream. The iron-chelated solutions function as a pseudo-
catalyst which can be regenerated. The H2 S is removed almost completely
and converted to elemental sulphur. After the absorption process a scrubber
is needed to remove the CO2 .
High pressure water scrubbing is based on the physical effect of dissolving
gases in liquids. In a scrubber, CO2 as well as the H2 S, dissolves into the
water while CH4 does not because of their difference in solubility. This makes
it a very simple process.
Pressure swing adsorption separates certain gas species from a mixture
of gases under pressure, according to the species’ molecular characteristics
and affinity for an adsorption material. The adsorption material adsorbs
H2 S irreversibly. Therefore a complex H2 S removal step is needed for this
process.
The fourth process separates the components cryogenically. The different
chemicals in biogas liquefy at different temperature-pressure domains allow-
ing for distillation. Typically a temperature of -170 ◦ C and a pressure of 80
bar is used.
Finally, it is possible to separate CO2 and H2 S from CH4 using a mem-
brane. Because of selective permeation, CO2 and H2 S will pass through a
certain membrane while CH4 does not. This is also a very simple technique
since only a compressor and a membrane are needed. The latter however is
expensive.

These techniques all have their unique advantages and disadvantages.

When an estimate of the costs for each technique has been made, an objective
comparison will be made.
Preface

This report presents the results of a multidisciplinary project executed at the

Technical University of Eindhoven commissioned by Dirkse Milieutechniek
BV (DMT). The results are also presented on a poster and a website.
The aim of such a project is to teach students, by means of real problems,
to combine and apply professional knowledge and skills and to integrate these
into non-technical aspects of importance and new technical knowledge. The
main goals are learning to communicate with colleagues from various fields,
and to gain experience in working as a team, executing a research project.
Dirkse Milieutechniek solves environmental problems with tailor made
solutions and is always seeking new possibilities to do so. DMT offers a wide
range of products and services varying from research, development, consul-
tancy and design to rental of equipment, installations service and mainte-
nance. DMT supplies equipment and systems for air treatment, odour abate-
ment, (bio)gas desulphurization, groundwater purification, soil remediation
and waste water treatment.
This project was focused on the upgrading of biogas. Biogas is a result
of anaerobic digestion of organic material, resulting in methane and carbon
dioxide gas and some pollutants. The methane gas can be used as a green
energy source by upgrading the biogas to natural gas and injecting it into
the existing gas grid. Upgrading of biogas signifies removal of the CO2 and
pollutants such as H2 S. Currently, several processes are available for the
upgrading.

Project description
Dirkse Milieutechniek is developing 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

• high pressure water scrubbing

• pressure swing adsorption

• cryogenic separation

• membrane separation

Firstly, each technique is described shortly including a cost estimate of the

final price per cubic meter of gas. Thereafter, a comparison of the advantages
and disadvantages of the different techniques is given. These results will help
Dirkse Milieutechniek decide which option to upgrade biogas best fits their
demands.

2
Contents

1 Introduction to Biogas 4

2 Upgrading techniques 6
2.1 Chemical absorption . . . . . . . . . . . . . . . . . . . . . . . 6
2.2 High pressure water scrubbing . . . . . . . . . . . . . . . . . . 8
2.3 Pressure swing adsorption . . . . . . . . . . . . . . . . . . . . 11
2.4 Cryogenic separation . . . . . . . . . . . . . . . . . . . . . . . 14
2.5 Membrane separation . . . . . . . . . . . . . . . . . . . . . . . 15

3 Comparison 18

4 Conclusions 19

Acknowledgement 21

Bibliography 22

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 such a renewable fuel, an energy source that can be applied in
many different settings. It is a combustible gas mixture produced by the
anaerobic fermentation of biomass by bacteria and takes only a relatively
short time to form. The gas mainly consists of combustible methane (CH4 ),
and non-combustible carbon dioxide (CO2 ). CH4 combusts very cleanly
without hardly any soot particles or other pollutants, making it a clean fuel.
In nature the fermentation process occurs in places where biological material
is fermented in an oxygen deprived environment such as swamps and wa-
terbeds. 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.
Besides CO2 , biogas also contains small amounts of hydrogen sulphide
(H2 S). When water is present, H2 S forms sulphuric acid (H2 SO4 ), which is
highly corrosive, rendering the biogas unusable. Currently, biogas which has
been stripped of H2 S is mainly used in gas turbines to produce electricity.
However, most energy is lost as heat in this process which results in a low
overall efficiency.

4
 The incombustible part of biogas, CO2 , lowers its calorific value. On
average, the calorific value of biogas is 21.5 M J/m3 whereas that of natural
gas is 35.8 M J/m3 . By removing CO2 from the biogas the calorific value is
increased. Stripping CO2 and H2 S from biogas is the so called upgrading of
biogas. By upgrading biogas to natural gas quality, containing approximately
88% CH4 , it is suitable for more advanced applications in which the heat is
not wasted, resulting in a higher efficiency. It is then applicable for use in
the gas grid and vehicles for instance.
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 neces-
sary to examine different upgrading methods to see which method might be
implemented in the industry. [1] [2]

5
Chapter 2

Upgrading techniques

This chapter gives a short description of the different techniques available to

upgrade biogas. For each technique, a short description including a diagram
is given, followed by the distinctive advantages and disadvantages of each
technique. Finally a cost estimate is given.

2.1 Chemical absorption

In the literature [3][4] several processes are presented that deal with removing
of H2 S. Many of them remove this pollutant only from the gaseous stream,
but do not convert H2 S into a more stable or valuable product, or convert
it into the elemental form sulphur (S). The conversion of H2 S into S or a
valuable compound is an advantage of chemical absorption with respect to
other methods.
The process of chemical absorption of H2 S into iron-chelated solutions
offers a high efficiency of H2 S-removal, the selective removal of H2 S and a
low consumption of chemicals because the iron-chelated solutions function
as a pseudo-catalyst that can be regenerated. The overall reaction of this
purification process is expressed as follows [5]:
1
H2 S + O2 (g) → S + H2 O (2.1)
2
In the reaction described above, H2 S is first being absorbed into water
and then undergoing the dissociation as follows:

H2 S(g) + H2 O
H2 S(aq) (2.2)
H2 S(aq)
H + + HS − (2.3)
HS −
H + + S 2− (2.4)

6
The formation of S occurs according to the following reaction mechanism:

S 2− + 2F e3+
S + 2F e2+ (2.5)
By means of oxygenation, the aqueous iron-chelated solution will be re-
generated. This oxygenation will be followed by conversion of the pseudo-
catalyst into its active form F e3+ . This mechanism is shown in the following
equations:

1 1
O2 (g) + H2 O(l) → O2 (aq) (2.6)
2 2
1
O2 (aq) + 2F e2+ → 2F e3+ + 2OH − (2.7)
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 [6]. 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 by ambient temperature.
Figure 2.1 shows an overview of the units that are used to test the H2 S
removal 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

Figure 2.1: Process flow diagram for chemical absorption of H2 S

7
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 on the
former page. The small particles of S that are formed, are separated from the
product stream in the particle separator. After this operation, 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
elementary form, so it can be sold to other companies. A big disadvantage
is that after the absorption process still a scrubber is needed to remove the
CO2 . It is not possible with this absorption process to get rid of the CO2 .
Currently, research is done on an absorption process with active coal as a
catalyst. This is however still in a beginning state, and will not be included
in this report.

Cost estimate
Work in progress

2.2 High pressure water scrubbing

Water scrubbing is a technique based on the physical effect of dissolving gases
in liquids. Water scrubbing can be used to remove CO2 and H2 S from biogas
since these components are more soluble in water than in methane. This ab-
sorption process is a pure physical process. In high pressure water scrubbing,
gas enters the scrubber under high pressure. Then, water is sprayed from
the top of the column so that it flows down counter-current to the gas. To
ensure a high transfer surface for gas liquid contact, the column can be filled
with packing material. After a drying step, the obtained methane purity can
reach 98% using this process. Figure 2.2 shows the flow diagram for high
pressure water scrubbing.

8
 Figure 2.2: Flow diagram for high pressure water scrubbing

There are two types of water scrubbing [7]:

Single pass scrubbing

In single pass scrubbing the washing water is used only once. The
advantage of this type of scrubbing is that there is no contamination
of the water with traces of H2 S and CO2 . This gives that the total
amount of CO2 and H2 S is at its maximum. The disadvantage of this
technique is that it requires a large amount of water. This technique is
only feasible when working near a sewer water cleaning plant of which
water can be used.

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.

Water scrubbing requires a large amount of water. For example, the re-
generative absorption process from DMT that washes 330 N m3 /hr biogas
requires around 1500 L/hr 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 use of such amounts of water.
Therefore, the main focus will be on regenerative absorption.

9
 When working at a 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 be a lot lower. Also, the washing water is over-saturated at atmospheric
pressure so regenerating will be a lot faster. The driving force behind the re-
generating process is the concentration difference between the over-saturated
concentration and the equilibrium concentration. With this being as high as
possible the speed of the process will be highest.
How much H2 S and CO2 can be dissolved is rather important for the
design of a water scrubber. The dissolubility of H2 S and CO2 increases with
increasing pressure. This relation can be described by Henry’s Law:

Pi = H · Cmax (2.8)

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
the same factor. This gives that the saturation concentration rises as well.
However, when higher pressures are reached the dissolubility of the com-
ponents will not linearly increase with the pressure. At higher pressures, the
increase of dissolubility becomes lower. Until a pressure of 20 bar the dissol-
ubility can be described according to Henry’s law [8]. These calculations are
based on the ideal situation so non-idealities should be taken into account
when designing the scrubber.
The mass transfer of components from the gas phase to the water phase
and vice versa is important to know. When this 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.
When two layers with different concentration profiles intersect, the fol-
lowing equations can be written:

NAG = kG · a · (CAG − CAGi ) (2.9)

NAL = kL · a · (CALi − CAL ) (2.10)

The mass transfer coefficients, kL and kG , are dependent on a lot of

parameters. It is difficult to get a precise measurement of these values. But

10
 Figure 2.3: Concentration profile in double film model

when there is a general idea of this value, the dimensions of the scrubber can
be designed.
When looking at the five techniques investigated, water scrubbing is the
simplest way to upgrade biogas. It is this simple because it only requires
water and an absorption column to upgrade the biogas. Scrubbers also have
some advantages [9] compared to other devices. Wet scrubbers are capable
of handling high temperatures and moisture. The inlet gases are cooled, so
the overall size of the equipment can be reduced. Wet scrubbers can remove
both gases and particulate matter and can neutralize corrosive gases.
Furthermore, water scrubbing can be used for selective removal of H2 S
because this is more soluble in water than CO2 . The water which exits the
column with the absorbed components can be regenerated and recirculated
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 elementary sulfur which causes operational problems.

Cost estimate
Work in progress

2.3 Pressure swing adsorption

Pressure swing adsorption (PSA) is another possible technique for upgrad-
ing of the biogas. PSA is a technology used to separate certain components

11
from a mixture of gases under pressure according to the species’ molecular
characteristics and affinity for an adsorption material. Figure 2.4 shows how
the adsorption material selects the different gas molecules. The adsorption
material adsorbs H2 S irreversibly and is thus poisoned by H2 S [10]. For this
reason, a H2 S removing step is often included in the PSA-process. Distur-
bances have been caused by dust from the adsorption material getting stuck
in the valves. Special adsorption materials are used as a molecular sieve, pref-
erentially adsorbing the target gas species at high pressure. 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.
(activated carbon, silica gel, alumina and zeolite). The process then swings to
low pressure to desorb the adsorbent material [11]. Desorbing the adsorbent
material leads to a waste stream, containing concentrations of impurities.

Figure 2.4: The principle of pressure swing adsorption, taken from [12]

The upgrading system consists of four adsorber vessels filled with ad-
sorption material, as can be seen in figure 2.5. During normal operation,
each adsorber operates in an alternating cycle of adsorption, regeneration
and pressure build-up. During the adsorption phase, biogas enters from the
bottom into one of the adsorbers. When passing the adsorber vessel, CO2 ,
O2 and N2 are adsorbed on the adsorption material surface. The gas leaving
the top of the adsorber vessel contains more than 97% CH4 . This methane-
rich stream is substantially free from siloxane components, VOC’s, water

12
 Figure 2.5: Flow diagram for pressure swing adsorption [12]

and has a reduced level of CO2 . Before the adsorption material is completely
saturated with the adsorbed feed gas components, the adsorption phase is
stopped and another adsorber vessel that has been regenerated is switched
into adsorption mode to achieve continuous operation. Regeneration of the
saturated adsorption material is performed by a stepwise depressurization
of the adsorber vessel to atmospheric pressure and finally to near vacuum
conditions. Initially, the pressure is reduced by a pressure balance with an
already regenerated adsorber vessel. This is followed by a second depres-
surization step to almost 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 adsor-
ber 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.

The main advantages of PSA are:

· A high CH4 -enrichment

· Low power demand
· Low level of emission

13
The main disadvantage of PSA is:

· H2 S needs to be removed prior to PSA

Cost estimate
Work in progress

2.4 Cryogenic separation

Cryogenic separation is a distillation process that demands cryogenic tem-
perature, which means low temperatures close to -170 ◦ C, and high pressure,
approximately 80 bar. Because CO2 , CH4 and all other biogas contaminants
liquefy at different temperature-pressure domains, it is possible to produce
pure CH4 from biogas. This is done by cooling and compressing the crude
biogas to liquefy CO2 which is then easily separated from the remaining gas.
The extracted CO2 can also be used as a solvent to remove impurities from
the gas.
Figure 2.6 shows the process flow diagram (PFD) of a cryogenic separa-
tion unit. This process flow diagram is made using the AspenTech program.
In this process the crude biogas is compressed to approximately 80 bar. The
pre-cooled compressed gas is dried to avoid freezing during the cooling fol-
lowing on the compression. The next step is the further cooling of the biogas
in chillers and series of linear heat exchangers to -45 ◦ C. Condensed CO2 is
removed in a separator. This CO2 is processed further to recover dissolved
CH4 which is recycled to the gas inlet. The gas is cooled further to ap-
proximately -55 ◦ C by heat exchangers. The cold gas is expanded through
a Joule-Thomson nozzle into an expansion vessel. The pressure in the vessel
is 8-10 bar and the temperature is approximately -110 ◦ C. In the expansion
vessel a gas-solid phase equilibrium is established. The solid phase is frozen
CO2 . The gas phase, which consists of more than 97% CH4 , is heated before
leaving the plant.

The main advantages of cryogenic separation are:

· Cryogenics can produce large quantities with high purity of the prod-
ucts.
· Expansion or reduction of product quantity by cryogenics processes,
i.e. scaling up, does not need new equipments in the process.
· The process makes no use of chemicals.

14
 Figure 2.6: Flow diagram for the cryogenic separation process

The main disadvantage of cryogenic separation is:

· Cryogenic processes require the use of numerous equipments and de-

vices, namely: compressors, turbines, heat exchangers, insulators, and
distillation columns. The need to maintain these equipments makes
from this separation technique a process with large capital costs. Con-
sequently, this technique becomes only economically feasible, if the sep-
aration of a large amount of biogas is needed.

Cost estimate
Work in progress

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
pressure between gases.

15
 Membrane gas separation modules can operate on the basis of selective
permeation [13]. The technology takes advantage of the fact that gases dis-
solve and diffuse into polymeric materials. If a pressure 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 coefficient. 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 hydro-
carbons including CH4 ). When a biogas stream containing 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 (A+B, depicted
below) is separated into a CO2 rich, low pressure permeate stream (B) and a
CO2 -depleted, high pressure natural gas stream (A). Depending on the mem-
brane, it is possible to also remove H2 S from the biogas making this process
favorable for upgrading biogas since no pre- or after-treatment is needed.

Figure 2.7: Schematic representation of membrane separation

Any polymeric material will separate gases to some extent. Proper selec-
tion of the polymeric material comprising the membrane is extremely impor-
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 [13]. Cellulose acetate is very inert and stable in CO2
hydrocarbon environments. Application of polyimide membranes has also
been found [14]. For this type of membrane, a single stage unit is sufficient
to achieve 94% enrichment from gas with a common concentration of CH4 .

16
 A higher pressure gives a higher gas flux through the membrane. How-
ever, the maximum pressure is determined by the membrane. For this reason,
high strength hollow fibre membranes have been developed. The efficiency of
the entire process mainly depends on the membrane. Its selectivity towards
the gases having to be separated, membrane flux or permeability, lifetime of
the membrane, maintenance and replacement costs are all factors that de-
termine the overall performance of such a biogas upgrading technique. An
overview of the main advantages and disadvantages is given below.

Advantages:

· Compactness and light in weight

· Low labor intensity
· Modular design permitting easy expansion or operation at partial ca-
pacity
· Low maintenance (no moving parts)
· Low energy requirements and low cost especially so for small sizes
· It requires no specific chemical knowledge
· Complex instrumentation is not required
· The basic concept is simple to understand

Disadvantages:

· Membranes are expensive

· Certain solvents can quickly and permanently destroy the membrane
· Certain colloidal solids, especially graphite and residues from vibratory
deburring operations, can permanently foul the membrane surface
· The energy costs are higher than chemical treatment, although less
than evaporation

Cost estimate
Work in progress

17
Chapter 3

Comparison

This chapter will contain the comparison of the different techniques.

18
Chapter 4

Conclusions

The explanation of the different techniques has yielded an idea of the possible
results of further research on these techniques. The costs of all different
processes will be estimated, which allows us to make a grounded and objective
comparison between these processes. The chemical absorption technique will
be extended with a part about absorption with active coal as a catalyst.
Currently, we suspect the chemical absorption process being a good option
for removal of H2 S. But an important disadvantage is the need of a scrubber
behind this process to get rid of the CO2 , because it is not possible to remove
CO2 with chemical absorption using an F e/EDT A catalyst.
The high pressure water scrubbing is found to be a relatively simple
process, compared to the other techniques. It can remove both H2 S and CO2
using a water stream, and can handle different temperatures and moisture
content. However, the amount of water that has to be used for this process
can become very large. This is an aspect we have to look at carefully during
the continuation of this research.
Pressure swing adsorption is already used in many upgrading processes.
It is a technique which results in a high CH4 -enrichment, without having a
lot of emissions while the needed power is relatively low. But, on the other
hand, when using this process, an extra step is needed to remove the H2 S.
The next process that is described is the cryogenic separation. This pro-
cess needs very low temperatures and high pressures and might therefore be
very expensive. Cryogenic separation is a technique that might be feasible
when a very large quantity of biogas has to be upgraded.

19
 Also membrane separation has been involved in our research. This tech-
nique does not require much instrumentation apart from the membrane and a
compressor. Both however, can be very expensive depending on the pressures
needed. Next to that, at this moment we do not know what the lifetime of
a membrane is in an upgrading process we are investigating. The feasibility
will therefore depend strongly on the costs of the membrane.
Comparing these techniques we can only speak about the theoretical pro-
cess information. To obtain more information for a grounded comparison we
will estimate the costs for each process.

Recommendations
Recommendations for future research will be given in the final report.

20
Acknowledgement

Thanking people for their support.

21
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[2] Information collected from DMT

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dade Estaldual de Maringá, 2001

[4] Astarita, G., Gioia, F., Hydrogen sulphide chemical absorption, Chemical
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[5] OBrien, M., Catalytic Oxidation of Sulfides in Biogas, Ventilation Air and
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[12] Dr. Alfons Schulte-Schulze Berndt, Intelligent Utilization of Biogas -

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22
[13] Natcogroup, Acid Gas (CO2 ) Separation Systems with Cynara Mem-
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[14] M. Harasimowicz, P. Orluk, G. Zakrzewska-Trznadel, A.G. Chmielewski,

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23