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Comparing different biogas

upgrading techniques
Final 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, July 3, 2008


Abstract

This report is the result of a multidisciplinary project at the technical uni-


versity of Eindhoven 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. This increases the concentration
of CH4 which gives the biogas a higher calorific value allowing for injection
in the gas grid or to use as a fuel. H2 S has to be removed because of its
corrosiveness.
Five techniques have been investigated. Chemical absorption of H2 S and
CO2 into iron-chelated cq. amine solutions offers a highly efficient removal
of H2 S from a gaseous biogas stream. The catalyst solutions function as
a pseudo-catalyst which can be regenerated. The H2 S is removed almost
completely and converted to elemental sulphur. The CO2 is removed and is
treated as a waste stream.
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, dissolve into the
water while CH4 does not, because of their difference in solubility. This
makes water scrubbing a very simple process.
Pressure swing adsorption separates certain gas species from a mixture of
biogas under pressure, according to the species molecular characteristics and
affinity for an adsorption material. The adsorption material adsorbs H2 S
either irreversibly or reversible. Therefore a complex H2 S removal step or
regeneration phase 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 -100 ◦ C and a pressure of 40
bars 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.
Each technique is compared on financial feasibility, impact on the envi-
ronment and ease of operating the process. Furthermore, each technique has
its own unique advantages and disadvantages. Table 1 gives an overview of
the costs, yield and purity of each technique.
Table 1: Comparison of prices, yield and purity of the different techniques
Technique Price per N m3 of biogas Yield Purity
€ % %
Chemical Absorption 0.28 90 98
High Pressure Water Scrubbing 0.15 94 98
Pressure Swing Adsorption 0.26 91 98
Cryogenic separation 0.40 98 91
Membrane separation 0.22 78 89

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.

Impact on the environment


Chemical absorption has several waste streams, one containing CO2 and
two different streams containing amines or F e/EDT A complexes.These are
the catalysts used in the absorption processes. All streams need to be dis-
posed as chemical waste. High pressure water scrubbing has two waste
streams. The water waste stream contains such a low concentration of H2 S
and CO2 that it does not need further treatment. The second waste stream is
a gas stream which also contains H2 S and CO2 but also some CH4 . Because
H2 S is rather poisonous, this stream should be treated and the CH4 should
be burned. Pressure swing adsorption and membrane separation both have
one waste stream that mostly contains CH4 and has to be burned. Cryo-
genics has also one waste stream containing mostly CO2 and some traces of
H2 S and CH4 . This waste stream needs treatment.

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

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


Eindhoven University of Technology commissioned by Dirkse Milieutechniek
BV (DMT). The results are also presented on a poster and a website
(http : //students.chem.tue.nl/if p24/).
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.
DMT solves environmental problems with tailor made solutions and is
always seeking new possibilities to do so. DMT offers a wide range of prod-
ucts and services varying from research, development, consultancy and de-
sign to rental of equipment, installations service and maintenance. DMT
supplies equipment and systems for air treatment, odor abatement, (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
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

• high pressure water scrubbing

• pressure swing adsorption

• cryogenic separation

• membrane separation

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


cost price per cubic meter of upgraded biogas. 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 customers demands.

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

A Alternate cost estimation PSA 41

B Cryogenic equipment 44

C CO2 footprint 46

D Visit to SMB Stortgas BV in Tilburg 49

E Visit to Carbiogas BV in Nuenen 51

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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 .

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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

Besides CO2 , biogas also contains small amounts of H2 S. H2 S is poi-


sonous when inhaled. Furthermore, when water is present, H2 S forms sul-
phuric acid (H2 SO4 ), which is highly corrosive, resulting in extra costs for
maintenance when using the biogas.
Depending on the source of the biogas, it can contain other pollutants.
Common pollutants are water vapor, ammonia (N H3 ) and siloxanes. Water
vapor in biogas forms, combined with N H3 or H2 S, a corrosive solvent.
Siloxanes are silicate compounds that have oxygen groups replaced by organic
groups like CH3 . When this compound is burned, it will form SiO2 (sand)
which can cause severe damage to equipment.
There are a number of uses for biogas. Currently, biogas which has been
stripped of H2 S is mainly used in gas turbines to produce electricity. How-
ever, most energy is lost as heat in this process, which results in a low overall
efficiency. But biogas can also be used for injection in the gas grid or as a
car fuel. The requirements for the end product depend on the final use of the
biogas. The average composition of gas in the gas grid for low calorific gas,
used in The Netherlands, and high calorific gas, used for example in Canada,
are shown in table 1.2 [2].
All of the values mentioned in table 1.2 are averages, except for the Wobbe
index. The Wobbe index of the gas should always be in between the men-
tioned boundaries. To reach the calorific value of Dutch natural gas the
methane purity should be increased to a value of 88%. But if Canadian stan-
dards must be achieved, as shown in table 1.2, the calorific value of biogas
should be increased above the calorific value of methane. This of course can
never be reached by increasing the purity of CH4 . Therefore, the purity of
CH4 should be as high as possible and some higher alkanes are added to the
gas to obtain the required calorific value. For injection of biogas into the gas
grid there are some additional requirements. These are shown in table 1.3
[2].

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Table 1.2: Average compositions of gas used in the commercial gas grid in The Nether-
lands and Canada

Dutch natural gas Canadian natural gas


Component (Source: Dutch Gas union) (Source: Uniongas Canada)
Volume % Volume %
Methane 81.30 94.9
Ethane 2.85 2.5
Propane 0.37 0.2
Butane 0.14 0.06
Pentane 0.04 0.02
Hexane 0.05 0.01
Nitrogen 14.35 1.6
Carbon Dioxide 0.89 0.7
Oxygen 0.01 0.02
Water vapor Unknown Unknown
Hydrogen Unknown Traces
Density (kg/m ) 3
0.833 0.7525
Wobbe index (M J/m3 ) 43.1-44.6 50.5-52.5
Calorific value (M J/m3 ) 31.669 37.8

The minimum amount of CH4 required as well as the maximum amount


of N2 depends on the Wobbe index. The Wobbe index is defined as follows:

calorif ic value(M J/m3 )


W obbe index = √ (1.1)
relative density
The Wobbe index is a measurement for the combustion behavior. If this
value is too high or too low, the combustion behavior will be disturbed. The
values may not deviate from the desired range.
Biogas can also be used as a car fuel. However, because of the low en-
ergy per volume the biogas must be compressed up to 200 bars. Also, the

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

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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].

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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:

Output = input · % CH4 · yield (2.2)


The total running costs are determined by the operating costs, the elec-
tricity and the water costs. The current electricity price is about € 0.10 per
kW h [13]. The price of water is € 0.92 per m3 [14]. The service costs are
€ 50,000 per year.

2.1 Chemical absorption


Both the chemical absorption of CO2 and H2 S were investigated.

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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

Figure 2.1: Process flow diagram for chemical absorption of CO2

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)

These aqueous solutions react with CO2 to absorb this component. In


open literature about chemical absorption of CO2 , no reliable information
about the reaction mechanism and kinetics is available. Therefore, the as-
sumption is made that the reaction mechanism occurs according to the ex-
perimental studies of Kumar, Hogendoorn, Feron and Versteegh, 2002. The
main reactions occurring during the absorption of CO2 are the following:

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.

2.1.2 Chemical absorption of H2 S


In the literature [7] [8] several processes are presented which discuss the
removal of H2 S. Many of these processes 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 highly efficient H2 S-removal, a 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 purifi-
cation process is expressed as follows [9]
1
H2 S + O2 (g) → S + H2 O (2.8)
2
In the reaction described above, H2 S is first absorbed into water and then
undergoes the dissociation as follows:

H2 S(g) + H2 O
H2 S(aq) (2.9)

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H2 S(aq)
H + + HS − (2.10)
HS −
H + + S 2− (2.11)

The formation of S occurs according to the reaction mechanism is described


here:

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.

Figure 2.2: Process flow diagram for chemical absorption of H2 S

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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.

Cost estimation for chemical absorption


For the absorption process, two cost prices of upgraded biogas are calculated,
one for the absorption of CO2 and one for the absorption of H2 S. The price
for biogas using both methods at the same time is calculated in the end.

Cost estimation chemical absorption of CO2


· one time per year general inspection in- and outside
· one time per year general inspection outside
· if necessary, cleaning of internals
· maintenance of recirculation pump
· calibration of instrumentation

Output: 137 N m3 /h, 1,127,000 N m3 per year


90% CH4 yield, purity output: 98% CH4

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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

Total investment costs € 353,000


Depreciation period of equipment is 10 years.

Running costs
Energy costs6 € 30,000
Catalyst costs5 € 50,000
Operator € 50,000
Maintenance6 € 4,500

Total running costs € 134,500

Costs per N m3 biogas without H2 S removal: € 0.17

After the absorption of CO2 , an amount of 3% H2 S is still present in the


biogas. For excellent cleaning of biogas, also the H2 S has to be removed,
because the requirements are less than 5 mg/N m3 biogas.

Cost estimation chemical absorption of H2 S


· one time per year general inspection in- and outside
· one time per year general inspection outside
· if necessary, cleaning of internals
· maintenance of recirculation pump
· calibration of instrumentation

Investment costs
Absorber column2 € 125,000
Additional costs6 € 100,000
2 Pumps3 € 10,000
Regeneration column1 € 90,000
Particle separator1 € 100,000

Total investment costs € 516,000

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Depreciation period of equipment is 10 years.

Running costs
Energy costs6 € 30,000
Catalyst costs5 € 15,000
Operator € 50,000
Maintenance6 € 4,500

Total running costs € 99,500

The costs per N m3 produced are calculated according to formula 2.1.


Costs per N m3 biogas: € 0.16

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:

Investment costs € 869,000


Running costs € 179,500

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

2.2 High pressure water scrubbing


Water scrubbing is a technique based on the physical effect of gases dissolving
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 CH4 . This
absorption process is a fully physical process. The main parts of the process
are shown in figure 2.3. In high pressure water scrubbing, gas enters the
scrubber at high pressure. This high pressure increases the dissolubility of
gases in water. 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 is usually filled with a packing material.

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]:

Single pass scrubbing


In single pass scrubbing, the washing water is used only once. The
advantage of this type of scrubbing is that no contamination in the
water occurs like 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 from
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


regenerative absorption process from DMT that washes 330 N m3 /h biogas

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:

NAG = kG · a · (CAG − CAGi ) (2.16)


NAL = kL · a · (CALi − CAL ) (2.17)

Figure 2.4: Concentration profile in double film model

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
a rough estimate of these values suffices to design the dimensions of the
scrubber.
Water scrubbing is a simple process because it only requires water and
an absorption column to upgrade the biogas. Scrubbers also have some
advantages [12] 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

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.

Cost estimation for high pressure water scrubbing


Output: 144 N m3 /h, 1,215,200 N m3 per year
94% CH4 yield, purity output: 98% CH4
Compressor (10 bars, 250 N m3 /h biogas) € 110,000
Columns /> € 140.000
Heat exchangers € 5,000
Pumps and blowers € 10,000
Total investment costs € 265,000
Depreciation period of equipment is 10 years.

Running costs
Energy costs € 60,000
Operator € 50,000

Total running costs € 110,000


Costs per N m3 biogas: € 0.13

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 .

2.3 Pressure swing adsorption


Pressure swing adsorption (PSA) is another possible technique for the up-
grading of biogas. PSA is a technology used to separate certain components
from a mixture of gases under pressure according to the species’ molecular
characteristics and affinity for an adsorption material. Figure 2.5 shows how
the adsorption material selects the different gas molecules. The adsorption
material adsorbs H2 S irreversibly and is thus poisoned by H2 S [15]. For this
reason, an H2 S removal 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 molecular sieves, 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
(for instance activated carbon, silica gel, alumina and zeolite). The process
then swings to low pressure to desorb the adsorbent material [16]. Desorbing
the adsorbent material leads to a waste stream, containing concentrations of
impurities.
The upgrading system consists of four adsorber vessels filled with ad-
sorption material, as can be seen in figure 2.6. 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 adsorbent material surface. This can be
seen in figure 2.5 where N2 , O2 , H2 O, H2 S and CO2 are adsorbed in the
adsorber. The gas leaving the top of the adsorber vessel contains more than
97% CH4 . This methane-rich stream is substantially free from siloxane com-
ponents, volatile organic compounds (VOCs), water and has a reduced level
of CO2 . Before the adsorbent material is completely saturated with the ad-
sorbed 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 adsorbent
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 ad-
sorber vessel. This is followed by a second depressurization step to almost

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]

things the remaining 3% CH4 ). CH4 is more damaging than CO2 , so it is of


most importance to make sure that CH4 is not emitted into the air. Burning
the CH4 is less harmful to the environment in comparison with emitting CH4
directly into the air. Therefore, the waste stream can be led to a gas engine
linked to a generator. Increasing the yield of CH4 in the product stream can
be achieved by recycling the waste stream. This has also a positive effect on
the amount of CH4 in the waste stream, which will decrease.

Cost estimation for PSA


Using the process flow diagram of the PSA-process, gives the following cost
estimation. The costs for the removal of H2 S are included in the investment
costs as well as in the running costs. The costs of the pressure swing ad-
sorption depend on which type of adsorbent 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 beginning in order to compress the incoming
biogas is the last element which contributes to the cost of the whole plant
significantly. Compression is expensive 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.
The type of adsorbent material used in the PSA is a carbon molecular

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.

Output: 139 N m3 /h, 1,176,000 N m3 per year


91% CH4 yield, purity output: 98% CH4

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

Total running costs € 187,250

The costs per N m3 produced are calculated as explained at the beginning of


this chapter.

Costs per N m3 biogas: € 0.25

2.4 Cryogenic separation


The name cryogenic separation already reveals the fact that this technique
makes use of low temperatures, close to -90 ◦ C, and high pressure, approxi-
mately 40 bars. Because CO2 , CH4 and all other biogas contaminants liquefy

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

Figure 2.7: A simple model of cryogenic separation of biogas. Streams 1, 2 en


3 respectively are the crude biogas (inlet gas), the upgraded biogas
(product) and the impurities.

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]

Biogas component Volume %


CH4 60
CO2 35
CO 0.15
N2 3
H2 1.55
H2 S 0.3
Oxygen, Siloxane traces

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

Cooler Compressor Cooler Compressor Cooler

Figure 2.8: Cooling and compressing units in cryogenic separation

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

Stream Inlet gas 1 2 3 4 5


Temperature (◦ C) 25 -70 207 -10 54 -10
Pressure (bar) 1 1 21 20 40 40
Vapor Fractions 1 1 1 1 1 1
Mass Flow (kg/h) 177.70 177.70 177.70 177.70 177.70 177.70
Volume Flow (m3 /h) 168.64 114.21 12.89 6.81 4.27 3.07
Enthalpy (M M kcal/h) -0.29 -0.30 0.28 -0.30 -0.29 -0.30

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.

Cost estimation for cryogenic separation


The cost analysis for the final designed process is estimated using quotations
from DMT, the Matches process, a cost engineering website (appendix B)
and Aspen Icarus process evaluator.

Output: 161 N m3 /h, 1,228,500 N m3 per year


98% CH4 yield, purity output: 91% CH4

26
Biogas
25 oC
1 bar
37 % CH4
58 % CO2
5 % other
Recirculation of product stream as cooling agent

-70 oC 207 oC -10 oC 54 oC -10 oC


1 bar 21 bar 21 bar 40 bar 40 bar -90 oC
40 bar
Cooler
Compressor Cooler Compressor Cooler
Distillation Column

Product Waste
91 % CH4 0.6 % CH4
8 % N2 98 % CO2
1% other

Figure 2.9: PFD of the cryogenic separation of biogas

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

Total investment costs € 908,500


Depreciation period of equipment is 10 years.

Running costs
Energy costs € 343,000
Operator € 50,000
Maintenance € 4,500
Total running costs € 397,500

Costs per N m3 biogas: € 0.44

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.

Figure 2.10: 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-

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

Figure 2.11: Schematic representation of an internally staged membrane separa-


tor

Cost estimation membrane separation


To prevent damage to the membrane, intensive pre-treatment might be nec-
essary. This could be quite expensive. However, it is not taken into account
in this report.

· 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

Total investment costs € 233,000


Depreciation period of equipment is 10 years.

Running costs
Energy costs (41 kW h) € 28,000
Operator € 50,000
Maintenance1 € 3,750

Total running costs € 81,750

The costs per N m3 produced are calculated as explained at the beginning of


this chapter.

Costs per N m3 biogas without H2 S removal: € 0.12

To remove H2 S the process described in 2.1.2 is added to these costs.


This results in a total cost price for upgraded biogas of € 0.22. This price is
calculated from the following values:

Investment costs € 749,000


Running costs € 126,750

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.

Impact on the environment


Looking at the amount of waste streams, it can be easily seen that pres-
sure swing adsorption and membrane separation have only one waste stream,
where chemical absorption and high pressure water scrubbing have two waste

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.

Technique Investment Running Cost price Maximum Maximum Advantages Disadvantages


cost cost upgraded achievable achievable
biogas yield purity
3
€ € €/N m biogas % %
Chemical ab- 353,000 134,500 0.17 90 98 · Almost complete H2 S re- · Only removal of one compo-
sorption moval nent in column
· Expensive catalyst

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 waste stream treatment is not considered in our investigation and


can influence the price of the upgraded biogas.

• For a better cost investigation more quotations should be acquired and


mass balances should be made. Then, a more precise estimation of the
cost per N m3 biogas can be made.

• The CO2 footprint is mentioned in the report but not calculated. When
mass balances are made the CO2 footprint can also be calculated.

• For chemical absorption it could be useful to look for more types of


catalyst.

• The performance of the membrane separation is highly dependent on


the type of membrane used. An investigation of more types of mem-
branes can be useful.

• Cryogenics is only investigated at one pressure and temperature. We


do not know if this is the optimal condition and therefore the cryo-
genics process should be investigated on a range of temperatures and
pressures.

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

[1] R. Lems, Biogasopwaardering: Het DMT-TS-PWS systeem, februari 2006

[2] Harry Benning, Opwerken van biogas naar aardgas kwaliteit, maart 2005

[3] Wahyudin, W., Biogas upgrading installation unit, 2007.

[4] Information collected from DMT

[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

[10] Wubs, H.J.and Beenackers, A.A.C.M., Kinetics of the Oxidation of Fer-


rous Chelates of EDTA and HEDTA into Aqueous Solutions, Ind. Eng.
Chem. Res., 1993, vol.32, pp2580 - 2594

[11] Perry, R.H. en D. Green, Perry’s chemical engineers handbook, McGraw-


Hill Book Company, USA, 6th print.

[12] Wikipedia, http : //en.wikipedia.org/wiki/W et_scrubber

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

[28] Carbon Trust, Carbon footprint measurement methodology, version 1.3,


march 2007

[29] R. Lems, Upgrading biogas, 2008

[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

Alternate cost estimation PSA

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:

OC Operating costs [E/year]


Qin Average inlet flow [N m3 /year]
W Theoretical work [J/m3]
EC Energy costs [E/J]

The energy input amounts to 1,875 kW h. The energy price per kW h


amounts to € 0.10. The operational costs become € 35,721-. The other part,
the capital costs, can now be calculated. These are divided in three parts.
The bed metal shell which includes the adsorber vessels, abbreviated with
CShell ; the costs of the compressor, CComp ; and finally, the costs of the driver
for the compressor, CDriver . The following equations are taken from [18].

CShell = P 0.584 · 4.93 · d · l + 3.74 · d2 + 739 (A.2)




Where:

P Pressure [P a]
d Bed diameter [m]
l Bed length [m]

The costs for the shell become € 425.500,-

CComp = 14.020 · Q0.435


in (A.3)

Qin Volumetric flow rate at the inlet [f t3 /min]

The costs for the compressors become € 79,423-.

CDriver = 11.68 · hp1.61 0.32


Comp + 2.470 · hpComp (A.4)

hpComp Horse power of compressor [hp]; assumed to be 5 hp.

The costs for the driver of the compressor become € 2,771-.

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

CCap Capital cost [E]


τpb Pay back time [s]
tax Tax rate [s]
Cop Operating cost [E]
dr Depreciation rate [−]

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,-.

The final cost price per N m3 biogas become: € 0,23.

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

The carbon footprint is a method to measure the effect of a certain process


on the environment in terms of the amount of green house gases produced
during the entire process. The process encompasses the whole life cycle of a
product, thus from the production of the raw material to disposal of the final
product. This makes it a very extensive method. In order to produce such
a carbon footprint, a certain path needs to be followed. This methodology
will be explained in the following text. Because of the method being that
extensive, the carbon footprint is not calculated for every biogas upgrading
technique separately.

Making a carbon footprint of a process will follow five major steps in


order to calculate the green house gases produced during the supply chain.
Table C.1 gives a schematic overview of the methodology.

Step 1 Analyze internal product data


Step 2 Build supply chain process map
Step 3 Define boundary conditions and identify data requirements
Step 4 Collect primary and secondary data
Step 5 Calculate carbon emissions by supply chain process steps
Table C.1: The overview of the five major steps in order to calculate the carbon
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]

Step 1: Analyze internal product data


The main goal of this first step is to develop a deeper understanding of the
product. This implies determining what raw materials the product is made
of and which actions or process are needed to convert the raw material into
the desired final product. Next to that, the waste streams and the produced
co-products have to be known. It is necessary carefully evaluate each step in
the entire process.

Step 2: Build supply chain process map


The objective of the second step is to produce the whole supply chain process
map, which can be visualized using figure C.1.

Step 3: Define boundary conditions and identify data requirements The


third step has two sub-objectives. First, the boundaries need to be set which
have to be followed for the product. After that, the required data is needed
in order to set up the mass balances and the carbon footprint.

Step 4: Collect primary and secondary data


From the data collected in the third step of the methodology, the required
data is found. This data can be used in order to develop the mass balance

47
and also to calculate the GreenHouse Gas emissions (GHG emissions) for
each step in the process.

Step 5: Calculate GHG emissions by supply chain process steps


Now all the required data is collected, a model can be designed to actually
calculate the mass balance and the GHG emissions of 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

Visit to SMB Stortgas BV in


Tilburg

Since 1987, DMT has grown to be a multidisciplinary international and lead-


ing company with important reference projects within the environmental
sector. DMT is expert in: air treatment and odor abatement systems, desul-
phurization unit (both biological and chemical), ground water purification
and soil remediation plants, water treatment plants and aeration systems
and water management. At this moment DMT is developing its biogas up-
grading technology. For SMB stortgas BV in Tilburg, a high pressure water
scrubbing plant is installed.
In Tilburg, a municipal association initiated a complex, including a land-
fill gas installation, a biogas plant, and an upgrading plant which has been
running since 1994. The upgraded gas, which has natural gas quality, is
injected into the natural gas network. An association has been created in-
volving 9 municipalities, of which Tilburg is the largest. The name is SMB
(Samenwerkingsverband Midden Brabant) and the objective is to solve the
waste problem in the cities. In total, the 9 municipalities have 480,000 inhab-
itants, who yearly produce 40,000 tons of organic waste. As a landfill biogas
treatment plant was already present in Tilburg, SMB chose anaerobic diges-
tion of the organic waste, which means Vegetable, Fruit and Garden waste,
(VFG) [30]. In order to obtain more detailed information about the upgrad-
ing processes of biogas and also to get answers to our questions regarding
this upgrading technique, we visited the SMB high pressure water scrubbing
plant in Tilburg. Our visit took place on the 9th of April 2008. We arranged
a meeting with René van den Kieboom. The visit started with a general
presentation about the upgrading plant in Tilburg, which was followed with
a detailed explanation about each separation unit. After this presentation
there was the opportunity for asking our questions. Since this excursion was

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

Visit to Carbiogas BV in Nuenen

Cirmac International BV is a world-wide operating company, specialized in


gas treatment systems for the petrochemical and chemical industry, refineries
and other industries. Cirmac is part of the Rosscor Group of companies.
In order to obtain more detailed information about the upgrading pro-
cesses of biogas, we visited an installation build by Cirmac on the 20th of
May 2008 in Tilburg at a site of Carbiogas BV. We arranged a meeting with
Ing. Olivier Kuijer and Ing. Maarten van den Heuvel in Nuenen.

Figure E.1: The VPSA plant in Nuenen

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