Clean Techn Environ Policy

DOI 10.1007/s10098-014-0787-7

ORIGINAL PAPER

Modeling and simulation of high pressure water scrubbing

technology applied for biogas upgrading
Petronela Cozma • Walter Wukovits •
Ioan Mămăligă • Anton Friedl • Maria Gavrilescu

Received: 12 September 2013 / Accepted: 12 May 2014

Ó Springer-Verlag Berlin Heidelberg 2014

Abstract Depending on the end of use, the quality of on the removal of undesired components from biogas were
biogas must be upgraded in order to utilize the maximum examined, based on modeling and simulation tools. For
amount of energy necessary for proper applications. simulation, the commercial software tool Aspen Plus was
Upgrading biogas refers to the increase of methane con- applied. Equilibrium model was applied for simulating the
centration in product gas by removal of CO2, which absorption process. The simulation results were validated
increases its heating power. Several treatment technologies with experimental data from the literature. The results are
are available for biogas upgrading: high pressure water summarized in terms of system efficiency, expressed as
scrubbing (HPWS), pressure swing adsorption, membrane CH4 enrichment, methane loss, and CO2 removal. Finally,
separation, chemical absorption, and gas permeation. Water new data which can be further applied for scale-up calcu-
absorption based on the physical effect of dissolving gases lations and techno-economic analysis of the HPWS process
in liquids (HPWS) is a well-known technology and the most are provided.
effective upgrading process, since provides a simultaneous
removal of CO2 and H2S. This could ensure an increasing Keywords Biogas upgrading  CO2 removal efficiency 
methane concentration and energy content per unit volume Gas absorption  Gas solubility  High pressure water
of biogas. In spite of this, few studies are published on scrubbing  Process simulation
biogas upgrading using pressurized water technology. In
order to elucidate the performance of HPWS technology at Abbreviations
industrial scale with the possibility of water regeneration AFR Air flow rate, Nm3/h
and recirculation, effects of different operating parameters CH4Recirc CH4 recirculated from flash back to crude
biogas (%)
CO2Recirc CO2 recirculated from flash back to crude
P. Cozma  M. Gavrilescu (&)
Department of Environmental Engineering and Management, biogas (%)
‘‘Gheorghe Asachi’’ Technical University of Iasi, 73 Prof. dr. CO2 RE CO2 removal efficiency (%)
doc. D. Mangeron Street, 700050 Iasi, Romania FWFR Fresh water flow rate (m3/h)
e-mail: mgav@ch.tuiasi.ro
GFR Plant capacity/gas flow rate (Nm3/h)
W. Wukovits  A. Friedl G Total gas flow rate (Nm3/h)
Institute of Chemical Engineering, Vienna University of HPWS Water scrubbing technology
Technology, Getreidemarkt 9/166, 1060 Vienna, Austria L Total liquid flow rate (m3/h)
M% Methane losses (%)
I. Mămăligă
Department of Chemical Engineering, ‘‘Gheorghe Asachi’’ Pflash Pressure in flash (bar)
Technical University of Iasi, 73 Prof. dr. doc. D. Mangeron Pstripper Pressure in stripper (desorber) column
Street, 700050 Iasi, Romania (bar)
Pabsorber Pressure in absorber column (bar)
M. Gavrilescu
Academy of Romanian Scientists, 54 Splaiul Independentei, PG Product gas which is equivalent to upgraded
050094 Bucharest, Romania biogas

123

SG Off gas from stripper
Tabsorber Temperature in absorber column (°C)
Tstripper Temperature in stripper (desorber)
column (°C)
VWFR/VGFR Volumetric water flow rate to gas flow
rate ratio (vol-based)
VFWFR/VGFR Volumetric fresh water flow rate to gas
flow rate ratio (vol-based)
VWFR/VWPA Volumetric water flow rate to water
pump-around flow rate ratio (vol-based)
VWPA/VGFR Volumetric water pump-around flow rate
to gas flow rate ratio (vol-based)
VAFR/VGFR Volumetric air flow rate to gas flow rate
ratio (vol-based)
XCO2 ;p¼10 Concentration of CO2 in liquid phase at
the equilibrium pressure of 10 bar
XCO2 ;p¼3 Concentration of CO2 in liquid phase at
the equilibrium pressure of 10 bar
YH2S,PG H2S content in product gas (vol%)
YCH4,PG CH4 content in product gas (vol%)
YCH4,SG CH4 content in off gas (vol%)
WFR Make-up water (% evaporated water per
hour of WPA) (m3/h)
WPA Water pump-around flow rate (amount of
recirculated water) (m3/h)
CH4 recirculated ð%Þ
V CH4 REC
¼  100;
VCH4 RICHSOL
CO2 recirculated ð%Þ
V CO2 REC
¼  100;
VCO2 RICHSOL
where VCH4 REC ; VCO2 REC —CH4 and
CO2 mol flow rate (kmol/h) at the top
exit of flash (GAS-REC stream; the
stream from flash recirculated back to
absorber);VCH4 RICHSOL ; VCO2 REC
CH4 and CO2 mol flow rate (kmol/h) at
the bottom exit of the absorber
VCH4 OFF GAS
Methane loss ð%Þ ¼  100;
VCH4 Raw biogas
where VCH4 is the CH4 mol flow rate
(kmol/h); the methane loss is expressed as
% of the outlet stream of stripper (off gas)
and inlet stream of biogas (raw biogas)
Introduction
Most of the biogas is produced during anaerobic digestion
of organic matter (e.g., manure, vegetable wastes, muni-
cipal solid waste, waste water etc.) (Cornea and Dima
123
P. Cozma et al.
2010; Jørgensen and Andersen 2012; Kapdi et al. 2005;
Petersson and Wellinger 2009; Puksec and Duic 2012).
However, both the biogas composition and the concentra-
tions of the contaminants are strongly dependent on the
type of waste or plant type used for the production of
biogas and on the season (Bruijstens et al. 2008; Cozma
et al. 2013a; Zagorskis et al. 2012). Usually, the CO2 and
H2S concentration in raw biogas varies from 30 to 50 vol%
and from 10 to 4,000 ppm, respectively. The usage of
biogas as a renewable energy source in combined heat and
power plants, as a transport vehicle fuel, or as a substitute
for natural gas has significantly increased in the last years
(Kismurtono 2011; Petersson and Wellinger 2009; Petter-
son 2013). Depending on the end of use, the quality of
biogas must be upgraded in order to increase its heating
value and to meet requirements for some gas appliances
(engines, boilers, fuel cells, vehicles) (Bauer et al. 2013;
Cozma et al. 2012; Mateescu et al. 2008; Petersson and
Wellinger 2009). Upgrading of biogas refers on increasing
methane concentration by removal of CO2 (Andriani et al.
2014; Cozma et al. 2012; Lems and Dirkse 2010; Starr
et al. 2012). There are some established technologies
applied for biogas upgrading based on: adsorption (pres-
sure swing adsorption), absorption (pressurized water
wash, physical or chemical absorption), membrane (high
pressure, low pressure) separation, cryogenic upgrading
(Balkenhoff and Jamieson 2008; Cozma et al. 2013a; Heile
et al. 2014; Shao et al. 2012).
Absorption with water or high pressure water scrubbing
(HPWS, where pressure is around 10 bar) is one of the most
common technique applied in an upgrading biogas plant for
simultaneous removal of CO2 and H2S, due to the lower
capital an operational cost implied, being a reliable and a
proven technology, simple and easy to maintain, without a
pre-treatment necessary (only if H2S content is low) (Cozma
et al. 2012; Eze and Agbo 2010; Hudde 2010; Kapdi et al.
2005; Lems and Dirkse 2010; Lombardi and Carnevale
2013; Ofori-Boateng and Kwofie 2009; Rasi et al. 2008).
Several studies were carried out on comparative cost analysis
of different types of technologies applied for biogas
upgrading (Anand et al. 2014; Jönsson 2010; Krich et al.
2005; Lems and Dirkse 2009; Ofori-Boateng and Kwofie
2009; Scholz et al. 2013; Teghammar et al. 2014). HPWS
was found to be one of the simplest and most economical
methods among the conventional one, such as chemical
absorption, membrane separation, pressurized swing
absorption, or cryogenic separation (Rasi et al. 2014).
However, when water is regenerated in a desorption column,
the energy consumption and costs are higher compared with
single pass scrubbing (Eze and Agbo 2010). In spite of this,
HPWS with regeneration of water is recommended to reduce
the amount of fresh water implied in the non-regenerative
HPWS process, since almost 100 times less water can be
Modeling and simulation of high pressure water scrubbing technology
consumed by a plant regenerating its water (Electrigaz
Technologies Inc. 2008; Starr et al. 2012).
HPWS provides simultaneous removal of CO2 and H2S
and product gas enrichment with CH4, since CO2 and H2S
are more soluble in water compared with CH4, N2, and O2
(Tippayawong and Thanompongchart 2010). Thus, physi-
cal absorption of gases in water is governed by Henry’s
Law, which implies an accurate knowledge of the solubility
of the main biogas components in water. This is an
essential condition for an optimum design and optimization
of HPWS process (Cozma et al. 2013a).
Although pressurized water scrubbing is a well-devel-
oped technology and increasingly implemented, especially
in EU members states, and plants in different sizes are
already commercially available (Cozma et al. 2012; Pet-
ersson and Wellinger 2009), there are few reports on the
related literature on operating and design parameters
affecting the performances of upgraded biogas using this
technology (Cozma et al. 2013b). In general, plant capac-
ity, the biogas and product gas composition, working
pressure, and in some cases make-up water values are the
basic data specified on a biogas upgrading plant (Cozma
et al. 2012). Gas absorption using HPWS is usually carried
out in packed-bed columns due to higher contact surface
area and effective mass and heat transfer provided by dif-
ferent types of packing materials. Packed-bed absorption
columns present various operational problems like high
pressure drop or flooding phenomena (Khan et al. 2011;
Sen et al. 2013). In order to achieve high CO2 removal
efficiency and methane enrichment, there is a need for
improved design of packed-bed absorption column and
optimization of operating conditions. Moreover, the rapid
increase in energy cost and the need of pollution control
and waste minimization often require the redesign and
optimization of an existing process (Bandyopadhyay 2011;
Gavrilescu 2008; Krallis et al. 2010).
Since there is a lack of models applied for HPWS process
and important data are not shown, it was considered oppor-
tune to develop simulation studies. These additional studies
will improve the plants functionality and elucidate the main
factors that influence the efficiency of the process (Santos
et al. 2013). In this manner, a basis for further research can be
provided. Simulation studies represent efficient way for
evaluation of different possible conversion processes as well
as to find optimum operation conditions for a given system
with respect to economic, safety, and environmental criteria
(Cozma et al. 2013b; Friedl et al. 1995, 2004). The optimi-
sation of parameters concerning physical absorption process
is necessary to obtain the maximum CO2 removal with low
methane loss at a minimum level of energy demand (Lantela
et al. 2012). More studies must be developed in order to
provide optimum performance, reliability, and low invest-
ments costs based on well-established operating and design
parameters necessary for scaling-up of water scrubbing
technology.
In this context, the main objective of the present study
was to simulate and evaluate the performances of HPWS
technology with regeneration and recirculation of water
applied for the removal of pollutants from biogas, in par-
ticular CO2, and to generate new data for scale-up calcu-
lations and techno-economic analysis of the process. There
are two main approaches to modeling absorber and strip-
per: equilibrium and rate-based approaches. Only the
equilibrium-stage approach is used in this study. All the
simulations were developed by commercial Software tool
Aspen Plus (V.7.1., 2009).
Solubility of gases in water
In the present study, the ability of some thermodynamic
models to calculate the solubility of the main biogas
components (CO2, CH4, H2S, N2, and O2) in pure water is
tested using Aspen Plus commercial software tool. The
results are compared with some relevant experimental data
from the literature.
In our study, we used a single standard flash unit with
varying operation conditions by changing the pressure and
temperature in the system. In addition, the following
thermodynamic models were tested: UNIQUAC (with ideal
gas and Henry’s Law), NRTL (non-random-two-liquid/
with ideal gas and Henry’s Law), NRTL-RK (non-random-
two-liquid/Redlich–Kwong equation of state with Henry’s
law), UNIQ-RK (UNIQUAC/Redlich–Kwong equation of
state with Henry’s Law); ELECNRTL (the electrolytic
non-random two liquids thermodynamic model with the
Redlich–Kwong equation of state for aqueous and mixed
solvent applications ? Henry’s law) (Aspen Physical
Property System 2010; Cozma et al. 2013a).1 The selection
of the models are supported by the fact that for the
absorption condition interests (low to medium pressures
and temperatures) no special EOS and/or mixing rules nor
fitting of interaction parameters are necessary to describe
the gas solubility (Cozma et al. 2013a).
Considering the importance of some gas–water systems
in the environmental protection, geological science, or
biological field, several experimental measurements have
been made by different authors on the solubility of binary
systems of carbon dioxide–water, methane–water, H2S–
water, nitrogen–water, and oxygen–water, over wide ran-
ges of pressures, and temperatures. Moreover, different
theoretical models for calculating the solubility of gases in
pure water were developed (Cozma et al. 2013a).
1
The paragraph has been adapted from Environmental Engineering
and Management Journal with permission of the Editor-in-Chief.
123
 P. Cozma et al.

Fig. 1 Solubility of biogas components in water: a CO2, b CH4, permission of the Editor-in-Chief) (Fig. 1b— literature compilation:
c H2S, d N2, e O2 (adapted upon Cozma et al. 2013a; reproduced from Stoessell and Byrne 1982; Mao et al. 2011)
Environmental Engineering and Management Journal with

Before simulation, a brief analysis regarding the available Before going into details on the results, the following
literature data on solubility of the main biogas components in aspects must be noted:
water was developed (data not shown; for more information
– the calculated data from Fig. 1a are compared with
please see the paper of Cozma et al. 2013a). Based on this
experimental data of Lide (1992);
analysis, the most relevant data were selected for each binary
– the solubility of CH4 in water is calculated using
system (carbon dioxide–water, methane–water, H2S–water,
experimental data of Chapoy (2004) and Chapoy et al.
nitrogen–water, and oxygen–water) and compared with our
(2004) and compared with experimental data of Mao
calculations. The results are plotted in Fig. 1.

123
 Table 1 Available literature data on biogas upgrading using HPWS with regeneration of water
Parameters Units Götz et al. Gryta Darmstadt Wixhausen DVGW R&D- DMT TS-PHPWSÒ Henriksdal Most likely
(2011) plant program ‘‘Biogas’’ Technology plant parameters

CH4/CO2 vol% 53.7/45.2 60–75/– 52/47 55.7/42.15 65/– 65/– 55–65/35–45

H2S/H2 ppm 101.8/508 \2,000/– \300/– –/– 1,500/– – 100–2,000
N2/O2/H2/H2O vol% 0.93/0.19 – –/B1/–/–/ 1.85/0.3/–/– – – –
Pabsorber bar 8/(6–17) 10 14 – 8–10 – –
o
Temperature C 20 – – – – – 20
Plant capacity (GFR) Nm3/h 242.3 – – 650 (m3/h) – 1,400 150–2,000
Make-up water (WFR) kg/h – – – – 500–5,000 – 500–5,000
AFR Nm3/h – – – – – – –
WPA m3/h 47.8 – – – – 210 –
Pflash bar 2–4 2–4 – – 2 – 2–4
Pstripper bar 1 – – – 1 – 1
VWFR/VGFR vol-based – – – – 0.002–0.0025 – –
VWPA/VGFR vol-based – – – – – – –
VAFR/VGFR vol-based 2.128/(0.13–0.32) – – – – – –
Results
Modeling and simulation of high pressure water scrubbing technology

CO2 RE [%] 98.96 – – 90.15 – – [97

M% 0.36 \2 0.8–1.8 \2 – \2
3
Treated flow rate Nm /h 133.9 – *150 – – – –
Upgraded biogas – – – – – –
CO2 mole fraction – – B 0.025 0.0415 \0.02 0.02 \0.02
CH4 0.968 [0.97 C0.97 0.916 [0.97 *0.97 C0.97
H2S 1 ppm – 0.7 ppm \1 ppm \3 ppm – \1 ppm
N2 0.021 – 0.033 – 0.01 0.01–0.033
O2 0.0056 – 0.0009 0.0078 – – 0.0009–0.0078
H2 – – – – – – –
H2O 0.0032 – – – – – –
Off gas – – – – – – –
CO2 mole fraction – – – 0.14–0.22 – – –
CH4 0.0007 – – 0.001–0.004 – – 0.0007–0.004
H2S 39.5 ppm – – 20–90 ppm – – 20–90 ppm
N2 0.652 – – 0.62–0.7 – – 0.6–0.7
O2 0.173 – – 0.16–0.19 – – 0.16–0.19
H2 – – – – – – –
H2O – – – – – – –

123

et al. (2011) and Stoessell and Byrne (1982); the
compilation of the last tow references is plotted in the
same line (Fig. 1b).
Taking into account the results from Fig. 1, the fol-
lowing aspects can be noted (Cozma et al. 2013a):
– the results from UNIQUAC and NRTL models did not
show a good agreement with the experimental CO2
solubility for pressures above 10 bar;
– NRTL-RK, UNIQ-RK, and ELECNRTL showed a
good agreement with experimental data in all condi-
tions presented.
As a main finding, the experimental data are accurately
reproduced by all the models applied under the conditions
of absorption interest (pressure up to 10 bar). NRTL and
UNIQUAC methods are proper for simulations pressures
up to 10 bar without including the critical region, as stated
by Carlson (1996). Therefore, NRTL model was chosen for
further analysis (Cozma et al. 2013a).
Simulation of physical absorption process applied
for biogas upgrading
Literature survey: available process data
Available literature data regarding HPWS technology with
the possibility of regeneration and recirculation of water is
very scarce (Table 1). In general, plant capacity, biogas
and product gas composition, working pressure, and in
some cases make-up water values are the basic data spec-
ified on a biogas upgrading plant. Moreover, an important
part of operating parameters affecting the efficiency of the
process (the quality of the upgraded biogas) is missing.
From these reasons, difficulties were encountered in
simulation of HPWS process using the experimental data
from the related literature. Basically, missing parameters
were estimated developing different sensitivity analysis
and taking into account the most important study of Götz
et al. (2011) from the literature.
Also, the DMT TS-PHPWSÒ was taken into account,
which is a guaranteed technology (with references since
1986) for removing of CO2, H2O, H2S, and various other
pollutants from biogas with minimal waste streams. At
different plant capacity from 250 to 2,000 Nm3/h, the
performances of this technology include (Dirkse 2010):
more than 97 % methane content in product gas, less than
2 % CO2 content, less than 2 % methane losses, high
efficiency on removal H2S in one step (\2 ppm in outlet
gas), low power consumption (0.4–0.5 kWh/m3 produced
gas), and high energy. Henriksdal biogas upgrading plant
from Stockholm, Sweden was initially built with a capacity
123
P. Cozma et al.
of 600 Nm3/h and was later extended to treat a total of
1,400 Nm3/h raw biogas. This plant improves the biogas
generated from the anaerobic digestion of sewage sludge
produced at Henriksdal sewage treatment plant (Balken-
hoff and Jamieson 2008). The biogas from Gryta waste
treatment plant is upgraded to fuel quality at Gryta biogas
upgrading plant which has a capacity of 150–550 Nm3/h
raw biogas (Växtkraft project 2004). DVGW R&D-pro-
gram ‘‘Biogas’’ takes part from DVGW Research Projects
(DVGW—Deutsche Vereinigung des Gas- und Wasserf-
aches e. V. - Technical and Scientific Association for Gas
and Water), which provides important data for biogas
production, biogas purification, and injection to the gas
grid from Germany (Graf and Klaas 2009). Graf and Klaas
(2009) from DVGW Research Station at Engler-Bunte-
Institut, Universität Karlsruhe analyzed the biogas com-
position from three plants with PSA, water scrubber and
one plant with a Genosorb scrubber. From this study, only
the data corresponding to HPWS technology are presented
in Table 1. The water scrubbing process implemented by
Darmstadt–Wixhausen was delivered by the company
Malmberg in Sweden. The calculations take into account
the gas quality and requirements for biogas injection
according to DVGW Gas quality G 260/G262.
Process description and process flow diagram
The operational conditions of the case study were estab-
lished based on data taken from the literature. The default
parameters are presented in Table 2 (Cozma et al. 2013b).
Figure 2 shows the flow diagram for pressurized water
scrubbing which involves the regeneration and recircula-
tion of water.
According to simulation studies presented in the first
part of paper, UNIQUAC and NRTL are in excellent
agreement at pressures up to 10 bar. Therefore, the NRTL
property method was used to describe physical absorption.
Absorber and stripper were modeled in Aspen using Rad-
frac modules without condenser and reboiler. The equi-
librium-stage approach in the gas–liquid system was used
for modeling the absorber and stripper units (Cozma et al.
2013b).
The simulated scrubbing process has been described
previously (Cozma et al. 2013b; Dirkse 2010; Petersson
and Wellinger 2009; Persson et al. 2006; Persson 2003)
(Fig. 2): after being pressurized to 10 bar (in the com-
pressors COMP1, COMP2), the incoming biogas contain-
ing 60 % CH4, 38.9 % CO2, 300 ppm H2S, 0.5 % N2, and
0.5 % O2 enters the bottom of the scrubber (ABSORBER),
while water is fed from the top of the column (LIQ-IN).
The technological process flow is alike to that descri-
bed previously (Cozma et al. 2013a, b): the CO2-enriched
water leaving the scrubber (RICH-SOL) is transferred to
Modeling and simulation of high pressure water scrubbing technology

Table 2 Specifications for Parameters Units Most likely parameters values Our default parameters
base-case simulation (based on the literature data) values (NRTL model)
(equilibrium calculations)
(Cozma et al. 2013b) CH4/CO2 vol% 55–65/35–45 60/38.97
H2S ppm 100–1,500 300
N2/O2 vol% 0.5/0.5
Pabsorber bar 8–10 10
Tabsorber °C 20 20
Tstripper °C 20 20
Plant capacity (GFR) Nm3/h 150–2,000 500
Make-up water (WFR) kg/h 500–5,000 2,000
3
Air flow rate (AFR) Nm /h 1,000
Water pump-around (WPA) m3/h 82.5
Pflash bar 2–4 3
Pstripper bar 1 1
Number of theoretical stages 7
L/GFR vol-based 0.2 0.169
VWFR/VGFR vol-based 0.0015–0.0045 0.004
VWFR/VWPA vol-based 0.0242
VWPA/VGFR vol-based 0.197 0.165
VAFR/VGFR vol-based 2 2
Comparison of the results from the literature with our results obtained through simulation
CH4,Recirc. to compressor (%) 94.065
CO2,Recirc. to compressor (%) 38.6
CO2 RE (%) [97 97.6
Methane loss (%) \2 0.313
Treated flow rate Nm3/h 309.36
Product gas (PG)
CO2 mole fraction \0.02 0.0093
The main available data are CH4 C0.97 0.967
taken from the existing
H2S \1 ppm 0.006 ppm
commercial plant, such as DMT
TS-PHPWSÒ Technology N2 0.01–0.033 0.0113
(Dirkse 2010); Henriksdal O2 0.0009–0.0078 0.00976
biogas upgrading plant from H2O 0.00228
Stockholm, Sweden
(Balkenhoff and Jamieson Off gas (SG)
2008); Gryta waste treatment CO2 mole fraction 0.157
plant (Växtkraft project 2004); CH4 0.0007–0.004 0.000767
DVGW R&D-program
H2S 20–90 ppm 123 ppm
‘‘Biogas’’ (Graf and Klaas
2009). Götz et al. (2011) study N2 0.6–0.7 0.647
is one of the most important O2 0.16–0.19 0.171
studies which provide important H2O 0.022
data on HPWS technology

the flash column (FLASH), where the pressure is reduced
from 10 to 3 bar in order to minimize methane loss. The
gas containing CO2, CH4, H2S, N2, O2, and water released
from the flash column (GAS-REC) is mixed with the raw
biogas (MIXER) and recirculated to the inlet of the
compressor (COMP2). After leaving the flash column, the
rich solution (SOL-FL) is sent to the desorption column
(STRIPPER), where it meets a counter flow of air (AIR-
STR), into which carbon dioxide and hydrogen sulfide are
released from water at regular atmospheric pressure and at
a temperature of 20 °C (GAS-EXIT). Subsequently, the
water is recirculated (LIQ-STR) back to the top of the
scrubber. Based on the initial process conditions, it was
calculated that the gas leaving the scrubber contains:
96.72 % methane, 0.937 % CO2, 0.006 ppm H2S, 1.1 %
N2, and 0.976 % O2. Methane loss is very low, that is
0.313 %. It is assumed that the water stream is recycled
continuously (in a closed loop), so that only 2 m3/h,
which means 2.4 % of circulating water flow rate (i.e.,
84.5 m3/h) is evaporated, or otherwise lost.

123

Fig. 2 Aspen Plus model for a biogas upgrading plant based on absorption with regeneration and recirculation of water (Cozma et al. 2013b)
Validation of the equilibrium model applied in this
study with the literature data
Götz et al. (2011) work is one of the most important studies
which provide important data on HPWS technology. There
is no other study in the literature to provide such detailed
data on the performance of HPWS process. Therefore, this
work was selected to validate the equilibrium-stage model
applied in the present study (Table 3) (Cozma et al.
2013b).
The authors studied the influence of pressure, regenera-
tion temperature, water pump-around consumption, air flow
rate, and other parameters on the HPWS technology applied
for biogas upgrading. The results are based on equilibrium
calculations using Aspen Plus software and validated by
real measurements. The authors used the ELECNRTL
thermodynamic method to describe the interactions of the
two-phase system. BINARY databank from available
Aspen data base was used to describe Henry’s coefficients.
The authors’ calculations take into account the gas quality
and requirements for biogas injection according to DVGW
Gas quality G 260 of ‘‘German Association of Gas and
Water Industry Directive.’’
In our study, validation of the equilibrium model was
achieved using the same working conditions reported by
Götz et al. (2011). Finally, the upgraded biogas and off gas
composition are compared in Table 3 (Cozma et al. 2013b).
Since the number of theoretical stages, as well as the
amount of fresh water inlet or the amount of water which is
continuously replaced due to the evaporation during the
process was not specified in Götz et al. (2011) work, we
developed a preliminary study to determine the minimum
number of stages and absorbent flow rate required to
achieve equilibrium. It was considered that only the water
lost due to evaporation was replaced, so that almost no
fresh water was used. Therefore, we considered a total
water flow rate of 47.8 m3/h, as mentioned in Table 3,
assuming that the water was completely recycled, since
123
P. Cozma et al.
only 1.5 % originating from the flow rate of the circulating
water was either evaporated, replaced during the process,
or otherwise lost. Our data showed that eleven theoretical
stages would be suitable in achieving equilibrium, and
nearly the same gas outlet composition as in the study of
Götz et al. (2011) will result. Since no significant errors
were found among the results of Götz et al. (2011) and ours
(Table 3), we concluded that this simulation is validated
and the associated data from Table 2 can be used for fur-
ther analysis (e.g., to simulate the HPWS technology)
(Cozma et al. 2013b).
Equilibrium approach
The first step of the present study consisted in theoretical
calculations of the number of stages and minimum and
optimum water flow rate necessary for the absorption
process in the conditions presented in Table 2 (default
parameters). The theoretical contact stages were deter-
mined graphically using the material balance for absorption
and gas–liquid equilibrium diagram. The minimum liquid
flow rate was also calculated taking into account the
equilibrium data of the system and the material balance.
Generally, in practice the optimum liquid flow rate is 1.5
times the minimum liquid flow rate (US EPA 2010).
According to calculations, six theoretical stages and an
optimum total water flow rate of 84.5 m3/h were necessary
to achieve an imposed CO2 RE (%) of 97 %, which is
equivalent with a final concentration of approximately
0.011 mol fraction CO2 in the upgraded biogas. In calcu-
lations, pure water was considered, therefore the initial
CO2 concentration in liquid phase was zero. Simulations
showed that a number of six stages are quite adequate to
achieve almost the desired CO2 RE (%) (the final CO2
concentration was 0.0165 mol fraction and removal effi-
ciency of *96). In these conditions, the methane content in
product gas was only 96 vol%. Because the water is
regenerated and recirculated it may also contain a small
Modeling and simulation of high pressure water scrubbing technology

Table 3 Operating parameters Parameters Units Götz et al. (2011) Our simulation
(literature versus our simulation
data) (Cozma et al. 2013b) CH4/CO2 vol% 53.7/45.2 53.62/45.2
H2S/H2 ppm 101.8/508 100
N2/O2/H2/H2O vol% 0.93/0.19 0.93/0.19/0.05/–
Pabsorber bar 8/(6–17) 8
Tabsorber °C 20 20
Tstripper °C 20 20
Plant capacity (GFR) Nm3/h 242.3
kmol/h 10.854
WFR (% evaporated water per hour of WPA) % 1–10 % 1.5 %
kg/h 720
AFR Nm3/h 515.6
kmol/h 23
WPA m3/h 47.8
kg/h 47,720
Pflash bar 3 3
Pstripper bar 1 1
Number of theoretical stages 11
L/GFR vol-based 0.2
VWFR/VGFR vol-based 0.003
VWFR/VWPA vol-based 0.015
VWPA/VGFR vol-based 0.197/(0.11–0.30) 0.197
VAFR/VGFR vol-based 2.128/(0.13–0.32) 2.128
Comparison of the results from Götz et al. (2011) with our results obtained through simulation
CO2 RE (%) 98.96 99.12
Methane loss (%) 0.36 0.326
Treated flow rate Nm3/h 133.9 134.35
Product gas (PG)
CO2 mol fraction 0.0047 0.00397
CH4 0.968 0.965
H2S 1 ppm 0.000094 ppm
N2 0.021 0.0209
O2 0.0056 0.00563
H2 0.000902
H2O 0.0032 0.00319
Off gas (SG)
CO2 mol fraction 0.175 0.171
CH4 0.0007 0.000677
H2S 39.5 ppm 38 ppm
N2 0.652 0.635
The figures in bold highlights
the similar performance of the O2 0.173 0.168
system, as obtained by G} otz H2 0.193 ppm
et al. 2011 and resulted from our H2O 0.0231 0.0234
simulation.

amount of CO2. Therefore, the initial concentration of CO2
in liquid will be somewhat greater than zero and the
number of theoretical stages could increase. Moreover, we
want to obtain higher methane concentration in the
upgraded biogas. Therefore, it was decided to increase the
number of stages at 7. It was assumed that water was
recycled continuously (closed system) and 2.4 % per hour
of circulating water (84.5 m3/h) was evaporated, otherwise
lost and replaced during the process.
The equilibrium model was used to evaluate the effects of
changing the most important operating parameters on pro-
cess efficiency. The results are summarized in terms of
system efficiency (assessment of CH4 enrichment, methane
loss, CO2 removal).

123
 P. Cozma et al.

Fig. 3 Influence of number of stages on a YCH4,PG (vol%) and M%, b CO2 RE (%), c YCH4,SG (vol%), d CH4,Recirc. (%) and CO2,Recirc.
(%), e YH2S,PG (vol%) (WFR = 2 m3/h; WPA = 82.5 m3/h; GFR = 500 Nm3/h; Pabsorber = 10 bar; T = 20 °C; Pflash = 3 bar)

Results of the simulation
Sensitivity analysis (equilibrium calculations): factors
affecting process efficiency
Theoretical number of stages
The influence of number of stages on methane content in
product gas (YCH4,PG (vol%)) and off gas (YCH4,SG
(vol%)), CO2 removal efficiency (CO2 RE (%)), CH4 and
CO2 recirculation (%), H2S content in product gas (YH2S,PG
(vol%)) at constant gas and water flow rate is presented in
Fig. 3. YCH4,PG (vol%) and CO2 RE (%) increased by
increasing the number of stages. Methane loss (M %) and
YCH4,SG (vol%) decreased from 0.47 to 0.288 and from
0.116 to 0.068 vol%, respectively, by increasing the number
of stages from 4 to 10. Due to relatively lower content of H2S
in raw biogas (300 ppm) almost a complete of its removal
was achieved. The results showed that YH2S,PG (vol%)
decreased from 0.783 to 3.39 9 10-11 ppm by increasing

123
Modeling and simulation of high pressure water scrubbing technology
Fig. 4 Influence of L/GFR ratio on a YCH4,PG (vol%) and M%, b CO2 RE (%), c CH4,Recirc. (%) and CO2,Recirc. (%) (seven equilibrium
stages; constant WFR of 2 m3/h; constant GFR of 500 Nm3/h; Pabsorber = 10 bar; T = 20 °C; Pflash = 3 bar)
the number of stages from 4 to 14. Further, the recirculation
of CH4 and CO2 increased from 92 to 94.47 and from 31.2 to
40.4 %, respectively, along with increasing the number of
stages.
Even if involves a simple dissolution of gases in water
under pressure, the absorption is a complex process.
Increasing the number of equilibrium stages favors the
absorption rate in water. More CO2 is dissolved and as a
consequence CO2 RE (%) and YCH4,PG (vol%) increased.
Methane loss decreases along with YCH4,PG (vol%)
increases. Moreover, it was observed that methane losses
will be lower if more amount of methane is recirculated.
On the other hand, increasing the number of equilibrium
stages favors also the desorption of CO2. At a constant
water flow rate and highest number of stages, the concen-
tration of CO2 in liquid phase is minimum since more CO2
will desorb. Since the concentration of methane in product
gas is maximum its concentration in off gas is minimum
(e.g., YCH4,SG (vol%) decreased from 0.116 to
0.068 vol% by increasing the number of stages from 4 to
10).
As discussed previously, increasing the number of
equilibrium stages increases the absorption rate in water,
but this will increase the manufacture and maintenance
costs as well, since a greater number of stages will require
a taller column. Therefore, an optimum number of stages
should be specified based on required amount of water
absorption and economic aspects. Taking into account that
the column absorption from the present study was designed
for *97 % CO2 removal efficiency, seven absorption
stages were chosen for further analyses.
L/GFR ratio
First, we should mention that L/GFR ratio must be greater
than a minimum established value. Thus, the minimum
total water flow rate of 56.31 m3/h (obtained according to
theoretical calculations) was multiplied by an k fac-
tor = 1.05; 1.1; 1.2; 1.3; 1.4; 1.5 in order to obtain the
maximum total water flow rate necessary to achieve
approximately 97 % RE of CO2. The amount of water
which is evaporated was kept constant (WFR = 2 m3/h)
and only the amount of recirculated water (WPA) was
varied. Increasing L/GFR ratio from 0.112 to 0.169 m3
H2O/Nm3 raw biogas improved gas purity but in the same
time increased methane loss (Fig. 4).
An increase of L/GFR ratio above the minimum value
(Lmin/GFR ratio) at constant number of stages led to an
123
 P. Cozma et al.

Fig. 5 Influence of fresh water flow rate to gas flow rate ratio (VFWFR/VGFR ratio) on a YCH4,PG (vol%) and M%, b CO2 RE (%) (seven
equilibrium stages; constant WPA of 84.5 m3/h; constant GFR of 500 Nm3/h; Pabsorber = 10 bar; T = 20 °C; Pflash = 3 bar)

Fig. 6 Influence of number of stages at different fresh water to gas flow rate ratio (VFWFR/VGFR ratio) values on a YCH4 and PG (vol%), b CO2
RE (%), c M%, d H2S,PG (ppm), and e CH4,Recirc. (%)

123
Modeling and simulation of high pressure water scrubbing technology

Table 4 Influence of biogas composition on process efficiency thus enhancing the CH4 content in PG from 96.796 to
Biogas composition YCH4PG M% CO2 RE CH4,REC
97.325 vol%, along with variation of VFWFR/VGFR ratio
CH4/CO2 (vol%) (vol%) (%) (vol%) from 0.002 to 0.016 m3/Nm3 raw biogas (Fig. 5). The H2S
concentration in PG decreased from 0.0058 to
55/43.97 92.45 0.158 88.37 96.29
0.00281 ppm, while N2 and O2 are not reduced in any
60/38.97 96.6 0.313 97.43 93.88 conditions (data not shown). We can observe also an
65/33.97 97.2 0.578 98.2 90.11 increase of M% with increasing of VFWFR/VGFR ratio. This
behavior is similar as in the case presented above (Fig. 4).
Therefore, the explanation is the same: the introduction of
Table 5 The influence of N2 and O2 amount on methane content in
product gas
larger quantities of water for absorption involves the dis-
posal of larger quantities of water from the system which
Components Biogas composition (vol%) PG composition contains more methane (LIQ-OUT stream). This explains
CH4 0.3987 0.0129 vol% the increases of methane loss along with VFWFR/VGFR ratio
CO2 0.6 0.978 vol% increase.
H2S 0.0003 0.00774 ppm Figure 6 shows the influence of number of stages on
N2 0.0005 0.00407 vol% product gas composition at different fresh water to gas flow
O2 0.0005 0.00252 vol% ratio values. Increasing both the amount of fresh water and
the number of stages increased the absorption capacity of
the system. It can be observed that YCH4,PG (vol%), CO2
RE (%), and YH2S,PG (vol%) increased with increasing
increase of CO2 removal efficiency. This means that lower both the number of stages and VFWFR/VGFR ratio. We
concentrations of CO2 in gas phase are released from should mention that above ten stages the product gas
absorber and the absorption rate in water increases. Since composition became constant. As expected, an increase of
YCH4,PG (vol%), CO2 RE (%), CH4,Recirc. (%), and water amount involves also an increase of M%. The
CO2,Recirc. (%) increase with increasing L/GFR ratio, we behavior is closely as in the cases presented in Figs. 4 and
rather expect in a decrease of methane loss. But we can 5. However, it should be noted that increasing the amount
observe a contradictory behavior, since M% increases of total water greater costs can be involved since larger
along with L/GFR ratio increase. This is because an amount of recirculated water implies higher energy
increase of L/GFR ratio also favors a higher retention of consumption.
CH4 in water. Even CH4 has a lower solubility in water
compared with CO2, some amount of CH4 is also dis- Biogas composition
solved, even more larger amounts of water are added. Thus,
methane is lost with liquid discharge from desorber (LIQ- The influence of biogas composition on methane content in
OUT stream). In other words, the introduction of greater product gas, CO2 RE (%), methane loss, CH4,Recirc. (%)
quantities of water for absorption involves the disposal of at constant water and gas flow rates, and seven equilibrium
larger quantities of water from the system which will stages is presented in Table 4. It can be observed that
contain more methane. This explains the increases of YCH4,PG (vol%), CO2 RE (%), and M% increased by
methane loss along with L/GFR ratio increase. varying biogas composition. Is obvious that having a lower
Most of the commercial upgrading plants are not able to initial concentration of CO2 in gas phase its removal effi-
recycle the water completely and so that almost 1–10 % of ciency will increase. By reducing the initial amount of N2
water is replaced every hour (Lantela et al. 2012; Persson and O2 from 0.5 to 0.05 vol%, the methane content in
2003). Even it was assumed that the water was recycled product gas increased as can be seen in Table 5.
continuously (closed system) and only the amount of
evaporated water is replaced, further analysis is focused on Pressure in absorber
adding different amounts of fresh water in the system,
besides the water evaporated, in order to increase the Further analysis is focused on testing the effect of different
absorption capacity of the column. pressure levels in the absorption column. Henry’s constant
The amount of recirculated water (WPA = 84.5 m3/h) is an indirect measurement of the solubilities of gases in
and number of stages were kept constant, while the amount liquids. In turn the solubility is influenced by temperature,
of fresh water was varied between 1 and 10 % from total pressure, and system type. The solubility decreases with
amount of 84.5 m3/h water. Increasing the amount of fresh increasing the temperature and increases with increasing
water increased the absorption capacity of the system. the pressure. It can be anticipated that CO2 RE (%) will
Actually CO2 RE (%) increased from 97.82 % to 99.217, increase by increasing the feed biogas pressure in the

123
 P. Cozma et al.

Fig. 7 Effect of working pressure on a YCH4,PG (vol%), b M%, c CO2 RE (%), d CH4,Recirc. (%) at different L/GFR ratio (7 equilibrium
stages; constant WFR of 2 m3/h; constant GFR of 500 Nm3/h; T = 20 °C; Pflash = 3 bar)

Fig. 8 Influence of temperature in absorber on a YCH4,PG (vol%) and M%, b CO2 RE (%), c CH4,Recirc. (%) and CO2,Recirc. (%)

123
Modeling and simulation of high pressure water scrubbing technology
Fig. 9 Influence of pressure in flash on a YCH4,PG (vol%) and M%, b CO2 RE (%), c CH4,Recirc. (%) and CO2,Recirc. (%)
absorption column because of the enhanced CO2 solubility
at higher pressures (Marzouk et al. 2010).
The effect of system pressure on CH4 content in product
gas, methane loss, CO2 RE (%), and the recirculation of CH4
at fixed gas and water flow rates (L/GFR = 0.169 m3 H2O/
Nm3 raw biogas) was investigated and the results are shown
in Fig. 7. Carbon dioxide removal efficiency increased with
increasing pressure, as expecting according to Henry’s law.
More CO2 is dissolved and as a consequence the methane
content in product gas (YCH4,PG (vol%)) increased.
Moreover, as the amount of methane in product gas
increased the methane loss decreased (M% is reduced from
0.817 to 0.274 % at pressures between 6 and 20 bar). At
pressures above 13 bar, the product gas composition became
constant. At 6-bar working pressure, higher amount of CO2
was found in product gas (81.864 kg/h or 0.12 mol fraction)
as at 17 bar (0.082 kg/h or 137 ppm CO2). The highest CH4
content of 97.7 vol% was obtained at 20 bar, while the CO2
removal efficiency was almost complete (99.96 %).
The effect of feed gas pressure in the absorption column
on product gas content at different water flow rates and
fixed gas flow rate (different L/GFR ratios) was also
studied. The results are combined with that from Fig. 7.
Actually, only the amount of recirculated water was
changed, and the WFR was kept constant at 2 m3/h. The
results indicated that a higher pressure could compensate
for lower absorbent flow rate since at 17 bar and lower
L/GFR ratio the amount of methane from PG is the same as
at 20 bar and higher L/GFR ratio. It can be noticed that a
significant reduction of methane loss is obtained at lower
L/GFR ratio and high pressure (at 20 bar the methane loss
was 0.09 %).
However, increasing the system pressure results in
higher power consumption by the raw gas compressors
(Lampert and Ziebik 2007), since gas compression is fol-
lowed by a sharp increase in temperature and an additional
gas cooling step is required, which adds to the overall
energy consumption.
Initial temperature in absorber
Solubility of gases in water and diffusion coefficients
varies with temperature (Moradi 2010; Sjöstrand and Yazdi
2009). Therefore, the solubility of gases in water decreases
by increasing the temperature, according to Henry’s law,
meanwhile the liquid-phase diffusion coefficients decrease
with decreasing the temperature (Moradi 2010), lowering
the CO2 removal efficiency. It should be noted that only the
inlet temperature of gas and water in absorption column
123

Fig. 10 Overall process mass balance at 3 bar pressure in flash (Cozma et al. 2013b)
was changed. The temperature in flash and stripper was
maintained at 20 °C.
Figure 8 shows the effect of temperature on CO2 RE
(%), YCH4,PG (vol%), M%, CH4,Recirc. (%), and CO2,-
Recirc. (%). As expected, CO2 RE (%) decreased by
increasing the temperature. Lower amounts of CO2 are
dissolved in water and as a consequence the methane
content in product gas decreased. Moreover, as the amount
of methane in product gas decreased the methane loss
increased. It is obvious that this behavior is vice versa
versus the effect of pressure levels in the absorber column.
Pressure in flash
The loss of methane is important both from economic and
environment point of view (Nozic 2006). Therefore, it is
essential to find the optimum combination of operating
parameters that will give the best results with regard to
methane loss, YCH4,PG (vol%) and CO2 RE (%). The
influence of the pressure in flash on methane content in
product gas, methane loss, CO2 RE (%), and the recirculation
of gas at fixed gas and water flow rates (L/
GFR = 0.169 m3 H2O/Nm3 raw biogas) are shown in Fig. 9.
The pressure in flash was varied from 2 to 10 bar. It can
be observed that YCH4,PG (vol%), M%, and CO2 RE (%)
increased by increasing the pressure in flash. The H2S
123
P. Cozma et al.
content in PG decreased from 0.153 to 0.002 ppm. N2 and
O2 content increased from 0.96 to 1.19 and from 0.829 to
0.998 %, respectively, by changing the pressure in flash
from 2 to 10 bar. In the exhaust gas, carbon dioxide content
ranged from 11.85 % to 15.64 vol%, methane content from
0.018 % to 1.63 vol%, H2S content from 0.0128 % to
0.012 vol%, nitrogen content from 67.8 to 63.5 vol%, and
oxygen content from 18 to 16.87 vol%.
The recirculation of gas is strongly dependent by the
pressure in flash, thus the recirculation of CH4 and CO2
decreased by increasing the pressure in flash. At 10-bar
pressure in flash, no CH4 or CO2 recirculation is involved,
but the methane loss is very high (6.72 %).
First, we should mention that the dependencies presented
above are obtained taking into account the calculations on
the entire system. At equilibrium conditions, a concentration
of CO2 in liquid phase exists which depends on pressure. At
pressure of 10 bar, the concentration of CO2 in liquid phase
ðXCO2 ;p¼10 Þ is higher compared to that at 3 bar ðXCO2 ;p¼3 Þ: At
the exit of flash, there are two phases: a liquid phase that
passes to desorber (SOL-FL) with the concentration
ðXCO2 ;p¼3 Þ which is much lower than at the inlet ðXCO2 ;p¼10 Þ
(RICH-SOL) and a gas phase which is recycled to absorber
(GAS-REC). A large decrease of pressure (in our case from
10 to 3 bar) resulted in large amount of recirculated gases
and to a decrease of efficiency. The pressure in flash was
Modeling and simulation of high pressure water scrubbing technology
chosen to be 3 bar to avoid the presence of large amounts of
methane in liquid phase. In other words, the liquid phase
from flash flows to stripper where desorption takes place
(methane is released from liquid phase and passes to gas
phase). Therefore, large quantities of methane can pass into
gas outlet of desorber if initially high amounts of methane
exist in liquid phase.
For a better understanding of the system behavior,
overall process mass balance at 3-bar pressure in flash is
shown in Fig. 10 (for more details on energy consumption
please see the paper of Cozma et al. 2013b).
After a brief analysis, the main conclusions of this
section can be drawn:
– the quality of the product gas (which contains 96.7 %
methane, 1 % CO2, 0.006 ppm H2S, 1.1 % N2, and
0.974 % O2) from this case study is suitable for vehicle
fuels since matches the requirements from the Swedish
Standard on biomethane SS 155438 ‘‘Motor fuels –
Biogas as fuel for high-speed Otto engines’’: CH4
97 ± 2 %; CO2 \4 %; CO2 ? O2 ? N2 max. 5 %;
– increasing the number of equilibrium stages increases
the absorption rate in water but this will increase as
well the manufacture and maintenance costs, since a
greater number of stages involves a higher column;
however, above ten stages the product gas composition
became constant; it should be noted that greater costs
could be involved since larger amount of recirculated
water implies higher energy consumption;
– increasing L/GFR ratio (m3 H2O/Nm3 raw biogas)
improved gas purity but in the same time increased
methane loss;
– the absorption capacity of the system increased along
with increasing the amount of fresh water;
– increasing the pressure in the absorber enhanced the
methane content in product gas and CO2 RE (%) but
also decreased the methane loss; however, with
increasing the pressure higher power consumption will
be registered by the raw gas compressors;
– higher pressure could compensate for lower absorbent
flow rate;
– it is a difficult task to find the optimum pressure in flash
since many factors must be considered; the methane
loss and energy consumption could be some important
factors to take into account;
– oxygen and nitrogen cannot be removed from raw
biogas using HPWS technology, moreover, their con-
centrations increased from 0.5 % to 1.1 vol% and
0.974 vol%, respectively, since fresh water is usually
saturated with these components;
– the presence of N2 in raw gas reduces the methane
content in product gas;
– the H2S content in the product gas was much less than
1 ppm almost in all the conditions studied.
For biogas upgrading process, it is important to find the
optimum combination of operating parameters that will
give the best results with regard to methane loss, YCH4,PG
(vol%) and CO2 RE (%) (Cozma et al. 2012).
Conclusions
Of all available biogas upgrading technologies with a high
potential to produce large amounts of upgraded biogas,
HPWS has been chosen for analysis in the present study.
This is a well-known technology and is currently the most
effective upgrading process. In spite of this, the related
literature provides very little information concerning the
influence of operating conditions and design parameters on
upgraded biogas composition.
We concluded that the equilibrium results showed that
biogas can be upgraded to 96.6 % methane content using a
counter-current HPWS process at 10-bar pressure and
20 °C temperature.
In this work, we have also discussed the procedures for
improving a biogas upgrading plant as well as the main
factors which influence the process efficiency. In this
manner, a basis for further research was provided. An
optimum combination of operating parameters must give
the best results with regard to methane content in product
gas, methane loss, and CO2 removal, taking into account
the energy consumption and the amount of water necessary
for absorption process. Further research in this area is
focused on the calculation of the rate of mass and heat
transfer between the gas and liquid phases, liquid and vapor
film diffusion or equipment hydrodynamics using the rate-
based model available in Aspen Plus simulation tool.
Acknowledgments This paper was carried out with the support of
EURODOC ‘‘Doctoral Scholarships for research performance at
European level’’ Project ID_59410, financed by the European Social
Found and Romanian Government. The support of the Institute of
Chemical Engineering - Vienna University of Technology, Austria in
using Aspen Plus software tool is highly acknowledged. This work
was partially supported by the Grant of the Romanian National
Authority for Scientific Research, CNCS – UEFISCDI, Project
Number PN-II-ID-PCE-2011-3-0559, Contract 265/2011.
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