Chemical Engineering Science 170 (2017) 639–652

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Chemical Engineering Science

journal homepage: www.elsevier.com/locate/ces

Performance evaluation of biogas upgrading by pressurized water

scrubbing via modelling and simulation
Christophe E. Wylock a, Wojciech M. Budzianowski b,c,⇑
a
Université Libre de Bruxelles, Transfers, Interfaces and Processes (TIPs), Av. F. Roosevelt 50, CP 165/67 - 1050 Brussels, Belgium
b
Consulting Services, Poleska 11/37, 51-354 Wrocław, Poland
c
Renewable Energy and Sustainable Development (RESD) Group, Poleska 11/37, 51-354 Wrocław, Poland

h i g h l i g h t s

Modelling of a scrubber-flash-stripper HPWS system for biogas upgrading.

A simulation procedure for optimized dimensioning of upgrading plant is proposed.

The influence of the water recirculation parameters on the scaling is studied.

Investigation of the operating and physico-chemical parameters on the performances.

a r t i c l e i n f o a b s t r a c t

Article history: The water scrubbing of biogas is an efficient, cheap and environmental friendly process to remove CO2
Received 11 July 2016 from biogas in order to upgrade it into biomethane. This work deals with the modelling and simulations
Received in revised form 12 November 2016 of a scrubber-flash-stripper high pressure water scrubbing process, which is currently the most mature
Accepted 9 January 2017
technology. The model and its associated simulation procedure can be used to estimate appropriate
Available online 10 January 2017
device sizes as well as to assess the performance of a given plant. Thanks to this tool, an optimized con-
figuration is computed for a reference case. A sensitivity analysis is also realized in term of scrubbing effi-
Keywords:
ciency and CH4 slippage. The influence of parameters related to the water recycling as well as the
Biogas
Biomethane
operating parameters is investigated. Moreover, the sensitivity of the model with respect to the solubility
Water scrubbing and transfer coefficient parameters is analyzed, in order to gain insight on the parameter to focus in the
Scrubber-flash-stripper configuration framework of a model calibration by experimental results.
Process scaling Ó 2017 Elsevier Ltd. All rights reserved.

1. Introduction explains why the generated biogas is commonly burnt in-situ by

Biogas is a renewable and sustainable fuel rich in methane
(CH4) generated through anaerobic digestion of organic matter.
Digestible organic materials may come from various sources: ded-
icated crops, agricultural residues, household wastes, water treat-
ment sludge’s, etc. Biogas is a potential substitute to natural gas
which attracts significant attention across countries importing fos-
sil fuels. However, such raw biogas is of low pressure, low specific
gravity and large specific volume. In addition, it contains a large
part of carbon dioxide (CO2), which lowers its calorific value, flame
velocity and flammability limits compared to natural gas. Besides,
the transport of CO2 diluted biogas over long distance is more
costly compared to e.g. natural gas pipeline transportation. This
⇑ Corresponding author at: Consulting Services, Poleska 11/37, 51-354 Wrocław,
Poland.
E-mail address: wojciech.budzianowski@gmail.com (W.M. Budzianowski).
combined heat and power (CHP) systems, which enables to convert
35–40% of biogas energy into usable electricity. A part of the
cogenerated heat is used for meeting the digester needs but most
is often dissipated and wasted because heat users are located far
from biogas CHP plants. The dilution of flue gases by combusted
CO2 makes it more difficult to recover energy of flue gases which
lowers thermal efficiency of biogas-fired CHP systems.
To overcome these issues, several processes have been created
over recent years to upgrade biogas into biomethane. Upgrading
basically relies on removing most of the CO2 and potentially other
trace compounds from the biogas (Sun et al., 2015; Abatzoglou and
Boivin, 2009; Ryckebosch et al., 2011; Budzianowski, 2012). Such
biomethane, which can be used directly as automotive fuel or
being injected into the natural gas grid, is claimed as an important
renewable fuel for Europe (Thrän et al., 2016).
The biogas upgrading processes are based on absorption,
adsorption, cryogenic or membrane technology (Beil and Beyrich,

http://dx.doi.org/10.1016/j.ces.2017.01.012
0009-2509/Ó 2017 Elsevier Ltd. All rights reserved.
640 C.E. Wylock, W.M. Budzianowski / Chemical Engineering Science 170 (2017) 639–652

Nomenclature

Latin k gas loss, Nm3/h

½ molar concentration, mol/m 3 q density, kg/m3
A interfacial area density, m1 # global mass transfer rate, kg/s
Cp specific heat capacity, kJ/(kg K) s mass transfer rate density, kg/(m s)
D diameter, m X column cross-section area, m2
D diffusive coefficient, m2/s
g gravity acceleration, m/s2 Subscript and superscript
H Henry constant, (Pa m3)/mol G gas phase
H height, m L liquid phase
kG transfer coefficient in the gas film, m/s in inlet
kL transfer coefficient in the liquid film, m/s out outlet
K chemical equilibrium constant CO2 carbon dioxide
KL liquid-side global mass transfer coefficient, m/s CH4 methane
M molar mass, kg/mol HCO 3 bicarbonate ion
pG gas total pressure, Pa CO2
3 carbonate ion
pG;i partial pressure of species i, Pa FLS flash tank
Q mass flow rate, kg/s RAW raw biogas
u superficial velocity, m/s SCR scrubber
T absolute temperature, K STR stripper
x mass fraction, kg/kg w pure water
y molar fraction, mol/mol r reaction
z vertical coordinate, m abs absorption

Greek
DE enthalpy variation, kJ/mol
g removal efficiency, %

2013). In this work we investigate the gas-liquid absorption by
water, called hereafter water scrubbing. Indeed, water is a cheap
and environmental friendly solvent for removing CO2. It makes
use of the higher solubility of CO2 (and other compounds like
H2S) than the solubility of CH4 in water. The ratio of Henry con-
stants between CO2 and CH4 is about 30 which makes water scrub-
bing of CO2 from biogas relatively efficient.
The most mature technology is the scrubber-flash-stripper high
pressure water scrubbing (SFS-HPWS), which is sketched in Fig. 1.
The CO2 capture from the biogas is performed in a scrubber, which
Fig. 1. Block-diagram of a scrubber-flash-stripper configuration of a pressurized
water scrubbing process.
commonly consists of a packed column. Due to the small CO2 sol-
ubility in water, the absorption rate is enhanced by setting its oper-
ating pressure between 0.8 and 1.2 MPa, in order to increase CO2
partial pressure in the biogas. This enables to reach high purity bio-
methane at the top of the scrubber. The dissolved CH4 within the
CO2-rich water leaving the scrubber is also increased under
elevated pressure operation. Therefore, the scrubbing solvent
needs to be subsequently separated in a flash tank operating at a
reduced pressure of about 0.11–0.2 MPa. The released gas, rich in
CH4 and CO2 is then mixed with the raw biogas and reinjected into
the scrubber. To regenerate the scrubbing water, the CO2 has to be
released. To achieve this solvent regeneration a second low pres-
sure packed column is used as a stripper. In this case, CO2 is des-
orbed from water at ambient temperature using air as stripping
agent. This considerably reduces energy requirements for solvent
regeneration compared to solvents with chemical compounds that
strongly bind CO2 and requires consequently higher stripping
temperature.
Several scrubber-flash-stripper HPWS plants already exist at
the commercial scale. Some examples of such plants as well as
their advantages and drawbacks are presented in Budzianowski
et al. (2017). Despite, it seems that very few HPWS models are pro-
posed in the literature. In addition, the available experimental data
are generally sparse and often focused only on the scrubber
analysis.
To scale appropriately the gas-liquid devices and the associated
equipment’s (pump, compressor, etc.) and to identify optimum
operating conditions for the process, mathematical modelling
and numerical simulation are particularly valuable to reach high-
performance SFS-HPWS plant. The industrially validated models
may be also useful in process control, including on-line monitoring
of plant performance. This work deals with the mathematical mod-
elling and the numerical analysis of the SFS-HPWS plant. The
appropriate column dimensions are related to the characteristics
of the biogas to upgrade (flow rate, concentration. . .), the targeted
 C.E. Wylock, W.M. Budzianowski / Chemical Engineering Science 170 (2017) 639–652 641

CO2 abatement and the effective transfer rates. The relevant trans-
fer phenomena are therefore described at the local scale to reach
reliable estimations of diameter, height and operating conditions
suitable for the plant scale.
Besides the model development, two procedures are proposed,
depending on the user’s goal: (1) scale a plant to ensure a given
HCO3 þ Hþ ð1Þ
performance or (2) evaluate the performance of a given plant oper-
ating with given conditions. This work notably analyses the influ-
HCO3 ð2Þ
ence of the parameters related to the scrubbing water recycling
on the scrubber and stripper sizes and the sensitivity of the perfor-
CO2
mance with respect to the operating conditions. It aims to get fur-
ther insight into the operations of SFS-HPWS plants by examining
Hþ þ OH ð4Þ
the trends and proposing some guidelines.
The developed model explicitly considers mass transfer
between gas and liquid and hence it is a so called non-
equilibrium rate based model which offers improved reliability in
simulations of mass transfer in biogas upgrading plants. A new
procedure for experimental model validation and calibration was
developed. Such models used with present-day computers will
be suitable tools for improving resource and energy efficiency of
processing industries. Their use will contribute to reducing indus-
trial emissions and making existing industries economically viable.
Also such models will allow for facilitated introduction of innova-
tive processes to the industrial practice at a very low cost. There-
fore, the present study can be considered as cutting edge
research in process engineering and science.
2. Mathematical modelling
2.1. Scrubber and stripper
It is well known that CO2 absorption in water is coupled with
chemical reactions: the dissolved CO2 may react with water mole-
cules and hydroxide ion (OH ) to form bicarbonate (HCO
3 ) and
carbonate (CO2
3 ) ions, according to the following scheme
(Danckwerts and Sharma, 1966; Cents et al., 2005; Danckwerts,
1970; Vas Bhat et al., 2000):
CO2 þ H2 O
CO2 þ OH
HCO3 þ OH
3 þ H2 O ð3Þ
H2 O
Nevertheless, due to the absence of any counter-ion, the pH of
scrubbing water is always below 7. The contribution of the reaction
(2) is very small due to the negligible OH concentration and the
reaction (3) is unlikely to occur. Only reaction (1) may have an
effect on the absorption rate. Its reaction rate is given by
Danckwerts and Sharma (1966), Cents et al. (2005) by kH2 O ½CO2 ,
with kH2 O  0.02 s1. This enables the estimation of its related
Hatta number (Trambouze and Euzen, 2002) by:
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
DL;CO2 kH2 O
Ha ¼ ð5Þ
kL
where DL;CO2 is the diffusive coefficient of CO2 in water and kL is the
liquid-side mass transfer coefficient, as defined in Table 1. Ha is
then estimated to 0.05, which is significantly smaller than the
threshold value 0.3. The reaction is therefore much slower than
the mass transport and it does not enhance the transfer. The effect
of the reaction rate is therefore neglected for the mass transfer rate
computation.
Despite the fact that the CH4 solubility in water is much smaller
than CO2, the high pressure used in HPWS induces a substantial
CH4 dissolution. The CH4 transfer may influence in the computa-

Table 1
Literature correlations used in the model.

Correlation References
Packing characteristics for 25 mm unglazed ceramic Intalox
saddle
dP = 25103 m Trambouze and Euzen (2002) (Tables 4.5 and 4.8)
AP = 250 m2/m3
F p = 320 m2/m3
rc = 61103 N/m
Henry coefficients
 
H CO2 ¼ 3:59  107 exp 2044
T
Versteeg and Van Swaaij (1988), in Vas Bhat et al. (2000), Wylock et al.
(2011)
  
H CH4 ¼ 1:3817  108 exp 1600 T1  298:15
1 Sander (1999)
Diffusive coefficients
 
DL;CO2 ¼ 2:35  106 exp  2119 Versteeg and Van Swaaij (1988), in Vas Bhat et al. (2000)
TL
h i1:8769 Guo et al. (2013)
DL;CH4 ¼ 1:95  109 229:8
TL
1

DG;CO2 ¼ 7:84 
T 1:75
105 pG Reid et al. (1986), in Wylock et al. (2014)
G

DG;CH4 ¼ 4:29 
T 1:5
104 pG Cowie and Watt (1971)
G

Equilibrium constants
 
K 1 ¼ exp  12092:1T  36:786lnðTÞ þ 235:482 qw Edwards et al. (1978), in Vas Bhat et al. (2000), Wylock et al. (2011)
K ¼ 10ð T þ22:4773logðTÞ61:2062Þ q2 Tsonopoulos (1976), in Vas Bhat et al. (2000), Wylock et al. (2011)
5839:5
w w
Column cross section area and pressure drop
qffiffiffiffiffi qffiffiffiffiffi
p2 ¼ uuGL qqL ¼ QQ GL qqG
G L
Trambouze and Euzen (2002) (Table 4.6)

ln p1;fl ¼ 0:1117  4:012p0:25

2
 0:2
p1 ¼ FgP qqG qqW llL
L L W
u2G
Mass transfer parameters

 0:75  uL qL 0:1 u2L qL 0:2 u2L APp 0:05 Onda et al. (1968), in Trambouze and Euzen (2002) (Table 4.7)
A ¼ AP 1  exp 1:45 rrc l AP rAP g
L

 1:33  0:5  0:33

kL 0:4 uL qL l u2L AP
AP DL ¼ 0:0051ðAP dP Þ l L AP
L
qL DL g
 0:7  
kG 2 uG qG lG 0:5
AP DG ¼ 5:23ðAP dP Þ l AP G q DG
G
642 C.E. Wylock, W.M. Budzianowski / Chemical Engineering Science 170 (2017) 639–652

tion of the CO2 molar ratio and it is necessary to evaluate the dis- where the locale value of Q G and Q L are computed from the inert
solved concentration in scrubbing water to control the flash tank gas and liquid conservation.
efficiency. The gas-liquid transfer of both CO2 and CH4 is therefore It is considered that gas phase follows the Raoult’s law, there-
considered. Their mass transfer rate density, sCO2 and sCH4 respec- fore a species partial pressure pG;i is directly deduced from its
tively, are computed according to the two-film theory (Whitman, molar fraction yG;i , which is related to its mass fraction by
1923) by the classical following expressions (Trambouze and yG;i ¼
x
P
G;i
xG;j . The total pressure of the gas pG is considered as a lin-
Mi
Euzen, 2002; Coulson and Richardson, 1999): j Mj

ear function of the column height. It is thus computed from the

sCO2 ¼ MCO2 A XK L;CO2 ðH CO2 pG;CO2  ½CO2 L Þ ð6Þ
sCH4 ¼ MCH4 A XK L;CH4 ðH CH4 pG;CH4  ½CH4 L Þ ð7Þ
A is the interfacial area density and X is the cross-section area
of the column. Mi , H i , pG;i , ½iL and K L;i denotes the molar mass, the
Henry constant, the gas bulk partial pressure, the liquid bulk molar
concentration and the liquid-side global mass transfer coefficient
of the species i, respectively. Eqs. (6) and (7) assume that CO2
and CH4 concentrations in gas and liquid phases are uniform at a
given column height.
The global transfer coefficients are computed as classically from
kG;i kL;i
the transfer coefficient in each phase by K L;i ¼ k
G;i þH i kL;i
, where kL;i
and kG;i are the transfer coefficient in the liquid and gas films,
respectively. It is assumed that water is not transferred (i.e. no
water evaporation neither condensation). The governing equations
of the scrubber/stripper models derive from the classical one-
dimensional global and species mass balances on an infinitesimal
element of the column height in both phases. The equations
describing the CO2 and CH4 mass flow rate evolutions in liquid
and gas phases write:
inlet gas pressure and the pressure drop induced by the packing
as pG ¼ pG;in þ DDpz z.
In the liquid phase, on the one hand, the concentration of the
dissolved CH4 is related its liquid mass fraction by
½CH4 L ¼ xCH4 ;L MqCHL , with qL the liquid density. On the other hand,
4
the dissolved CO2 takes part to reactions. Although the reactions
do not induce any transfer rate enhancement, they may have an
influence by modifying the actual CO2 concentration. ½CO2 L is not
directly deduced from the total dissolved CO2 mass fraction
xL;CO2 ; , because a small fraction of CO2 is converted into HCO3.
The dissolved CO2 is shared according to:
qL
xL;CO2 ¼ ½CO2 L þ ½HCO3 L ð18Þ
MCO2
Considering that the chemical equilibria are reached in the bulk
of liquid phase at steady-state anywhere the column, ½CO2 L is com-
puted from xL;CO2 using the equilibrium expression
½HCO3 L ½Hþ L
K1 ¼ ð19Þ
½CO2 L

dðQ G xG;CO2 Þ dxG;CO2 dQ G and the electroneutrality equation neglecting the OH concentra-
¼ QG þ xG;CO2 ¼ sCO2 ð8Þ tion, leading to:
dz dz dz
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi

ffi!
dðQ G xG;CH4 Þ dxG;CH4 dQ G qL 1 qL
¼ QG þ xG;CH4 ¼ sCH4 ð9Þ ½CO2 L ¼ xL;CO2  K 1 þ K 1 4xL;CO2 þ K1
dz dz dz MCO2 2 M CO2
ð20Þ
dðQ L xL;CO2 Þ dxL;CO2 dQ L
¼ QL þ xL;CO2 ¼ sCO2 ð10Þ
dz dz dz
2.2. Flash tank
dðQ L xL;CH4 Þ dxL;CH4 dQ L
¼ QL þ xL;CH4 ¼ sCH4 ð11Þ The flash tank is modelled as a perfectly mixed continuous
dz dz dz
device, with one inlet (the liquid leaving the scrubber) and two
z is vertical coordinate in the column, Q denotes the mass flow
outlets (the gas returning to the scrubber and the liquid
rate and x the mass fraction.
entering the stripper). The following simplifications are assumed:
Since the inert part of the gas and liquid flow rates,
(i) the separation between the phases is perfect (no liquid is
Q G ð1  xG;CO2  xG;CH4 Þ and Q L ð1  xL;CO2  xL;CH4 Þ respectively,
entrained by the gas), (ii) the thermodynamic equilibrium is
remains constant, the two following equations can be derived:
reached instantaneously between the gas and the liquid, (iii) the

dxG;CO2 dxG;CH4 dQ G pressure drop induced by the expansion is negligible (pFLS is con-
Q G þ þ ð1  xG;CO2  xG;CH4 Þ ¼0 ð12Þ
dz dz dz stant), (iv) the flash temperature is constant (isothermal), (v) the
water vapor content in the gas is negligible since the temperature

dxL;CO2 dxL;CH4 dQ L is low.

Q L þ þ ð1  xL;CO2  xL;CH4 Þ ¼0 ð13Þ The governing equations of the proposed model include
dz dz dz
therefore:
By injecting Eq. (12) in Eqs. (8) and (9) and Eq. (13) in Eqs. (10)
and (11), they reduce to:
Q L;in xL;CO2 ;in ¼ Q L;out xL;CO2 ;out þ Q G;out xG;CO2 ;out ð21Þ
dxCO2 ;G sCO2 ð1  xCO2 ;G Þ þ sCH4 xCO2 ;G
¼ ð14Þ
dz QG Q L;in xL;CH4 ;in ¼ Q L;out xL;CH4 ;out þ Q G;out xG;CH4 ;out ð22Þ

dxCH4 ;G sCH4 ð1  xCH4 ;G Þ þ sCO2 xCH4 ;G Q L;in ð1  xL;CO2 ;in  xL;CH4 ;in Þ ¼ Q L;out ð1  xL;CO2 ;out  xL;CH4 ;out Þ ð23Þ
¼ ð15Þ
dz QG
xG;CO2 ;out þ xG;CH4 ;out ¼ 1 ð24Þ
dxCO2 ;L sCO2 ð1  xCO2 ;L Þ þ sCH4 xCO2 ;L
¼ ð16Þ
dz QL ½CO2 L;out ¼ H CO2 pG;CO2 ;out ð25Þ

dxCH4 ;L sCH4 ð1  xCH4 ;L Þ þ sCO2 xCH4 ;L ½CH4 L;out ¼ H CH4 pG;CH4 ;out ð26Þ
¼ ð17Þ
dz QL
 C.E. Wylock, W.M. Budzianowski / Chemical Engineering Science 170 (2017) 639–652 643

2.3. Model parameters the resulting liquid flow rate leaving the scrubber is then deduced by
1xCO
2 ;L;in;SCR
Q L;out;SCR ¼ Q L;in;SCR 1xCO xCH
.
2 ;L;out;SCR 4 ;L;out;SCR
The expressions correlating the packing characteristics and the
Eqs. (21)–(26) are solved numerically using Q L;in;FLS ¼ Q L;out;SCR ,
physico-chemical are found in the literature. They are presented in
Table 1. xCO2 ;L;in;FLS ¼ xCO2 ;L;out;SCR and xCH4 ;L;in;FLS ¼ xCH4 ;L;out;SCR , with the routine
It is worth to mention that the correlations used for the transfer fsolve, to compute Q G;out;FLS , Q L;out;FLS , xCO2 ;G;out;FLS , xCO2 ;L;out;FLS ,
coefficients are the correlations of Onda et al. (1968), which were xCH4 ;G;out;FLS and xCH4 ;L;out;FLS . The new values of Q G;out;FLS , xCO2 ;G;out;FLS
developed from experimental data for various liquids and operat- and xCH4 ;G;out;FLS are then used to realize a new iteration. This loop
ing conditions. Even though some recent works like Nock et al. is realized until the variations between two successive iterations
(2014) tend to show that the more recent correlations of Billet become slower than a given tolerance.
and Schultes (1993) are slightly better, the correlations of Onda Once the steady-state is reached, the eventually obtained
et al. remain the most commonly used for several industrial pro- Q L;in;SCR is used to calculate the requested scrubber diameter DSCR
cesses. The accuracy depend on the system studied and for exam- for the corresponding superficial velocities in the considered pack-
ple in the system ammonia-carbon dioxide-water-air similar to ing. The diameter is such that the superficial gas velocity corre-
that of the current study the correlation of Onda et al. was found sponds to 60% of the flooding one and it is calculated thank to
the most accurate from several correlations compared the correlations presented in Table 1.
(Budzianowski and Kozioł, 2006). Finally, the minimum scrubber height, HSCR , is estimated by
solving Eqs. (14)–(17) with the ode15s routine, from the bottom
to the top of the scrubber. A much larger height is used as an initial
3. Simulation procedure
guess. HSCR is identified as the height matching the outlet criterion,
i.e. xCO2 ;G;SCR ðHSCR Þ ¼ xCO2 ;G;out;SCR .
The simulations are performed using the computational soft-
ware Matlab. The model can be used to estimate appropriate
device size for reaching a given performance as well as to compute 3.1.2. Stripper
the performance of a given plant. Since the composition of the air injected at the stripper inlet are
known (xCO2 ;G;in;STR ¼ 6  104 , corresponding to the molar ratio of
3.1. Plant scaling 0.04% in the atmospheric air), it is required to impose only the
CO2 mass fraction to reach at the stripper outlet xCO2 ;G;out;STR . The
This procedure is used if the goal is to determine the required global CO2 stripping rate to achieve is calculated as
scrubber and stripper sizes, scrubbing water flow rate and strip- #CO2 ;STR ¼ Q L;in;SCR xCO2 ;L;in;SCR  Q L;out;FLS xCO2 ;L;out;FLS . The needed inlet
ping air flow rate for reaching an imposed CO2 abatement at the 1xCO
2 ;G;out;STR
scrubber gas outlet. In this case, three regulation parameters air flow rate is then deduced by Q G;in;STR ¼ #CO2 ;STR xCO xCO
.
2 ;G;out;STR 2 ;G;in;STR

related to the scrubbing water recycling have to be specified: the Knowing the gas and liquid flow rates, the stripper diameter
CO2 mass fraction in the water entering and leaving the scrubber and height, DSTR and HSTR respectively, are estimated using the
and in the stripping air leaving the stripper: xCO2 ;L;in;SCR , xCO2 ;L;out;SCR same procedure than for the scrubber. The estimated HSTR is the
and xCO2 ;G;out;STR , respectively. height matching the condition xCO2 ;L;SCR ðHSCR Þ ¼ xCO2 ;L;out;SCR , with
The scaling is realized in two stages. The first one computes the xCO2 ;L;out;SCR ¼ xCO2 ;L;in;SCR .
characteristics of the scrubber in coupling with the flash tank.
Since the gas entering the scrubber is a mixture between the raw
biogas to treat and the gas leaving the flash tank, which depends 3.2. Performance computation
on the composition of the liquid leaving the scrubber, several iter-
ations of the scrubber-flash loop are performed to compute the Whether the scrubber and stripper diameters and heights are
streams at steady-state. The second stage computes the stripper known and the scrubbing water and stripping air flow rates are
characteristics taking into the liquid stream coming from the flash imposed, or has been estimated by the plant scaling procedure,
tank and the CO2 depletion to reach for reinjection in the scrubber. the performance of each unit of the plant are computed. Due to
scrubbing water recycling, several iterations of the process are
3.1.1. Scrubber-flash realized to ensure the steady-state at a given tolerance.
The actual gas flow rate entering the scrubber is At each iteration, the outlet variables of each unit are computed
Q G;in;SCR ¼ Q G;RAW þ Q G;out;FLS and its composition is given by according to their inlet variables, with the following sequence.
xCO2 ;G;in;SCR ¼ ðQ G;RAW xCO2 ;G;RAW þ Q G;out;FLS xCO2 ;G;out;FLS Þ=Q G;in;SCR and The gas mixture at the scrubber gas inlet is given
xCH4 ;G;in;SCR ¼ ðQ G;RAW xCH4 ;G;RAW þ Q G;out;FLS xCH4 ;G;out;FLS Þ=Q G;in;SCR . At the by Q G;in;SCR ¼ Q G;RAW þ Q G;out;FLS , xCO2 ;G;in;SCR ¼ ðQ G;RAW xCO2 ;G;RAW þ
first iteration, Q G;out;FLS ¼ xCO2 ;G;out;FLS ¼ xCH4 ;G;out;FLS ¼ 0 can be used Q G;out;FLS xCO2 ;G;out;FLS Þ=Q G;in;SCR and xCH4 ;G;in;SCR ¼ ðQ G;RAW xCH4 ;G;RAW þ
as initial guesses. Q G;out;FLS xCH4 ;G;out;FLS Þ=Q G;in;SCR . The characteristics of the liquid inlet
Let xCO2 ;G;out;SCR be the targeted mass fraction to reach at the gas are given by the imposed Q L;in;SCR and by xCO2 ;L;in;SCR ¼ xCO2 ;L;out;STR
scrubber outlet. As an approximation, it can be considered that only and xCH4 ;L;in;SCR ¼ xCH4 ;L;out;STR . The evolution profiles of xCO2 ;G;SCR ,
CO2 is transferred from gas to liquid. Therefore, the global CO2 xCH4 ;G;SCR , xCO2 ;L;SCR , xCH4 ;L;SCR , Q G;SCR and Q L;SCR along the height HSCR
scrubbing rate can be estimated #CO2 ;SCR ¼ Q G;in;SCR are computed by solving Eqs. (14)–(17) with the bvp4c routine,
 
1xCO ;G;in;SCR
1  1xCO ;G;out;SCR . By imposing the CO2 mass fraction in the water
2 enabling the determination of the outlet variables xCO2 ;G;out;SCR ,
2 xCH4 ;G;out;SCR , xCO2 ;L;out;SCR , xCH4 ;L;out;SCR , Q G;out;SCR and Q L;out;SCR .
at the inlet and the outlet of the scrubber, xCO2 ;L;in;SCR and
At the first iteration, Q G;out;FLS ¼ xCO2 ;G;out;FLS ¼ xCH4 ;G;out;FLS ¼ 0 and
xCO2 ;L;out;SCR , respectively, the requested flow rate is estimated by
1xCO xCO2 ;L;in;SCR ¼ 7  107 and xCH4 ;L;in;SCR ¼ 4  1012 (corresponding to
2 ;L;out;SCR
Q L;in;SCR ¼ #CO2 ;SCR xCO ;L;out;SCR xCO ;L;in;SCR
. Considering that the dissolved the composition at equilibrium with the CO2 and CH4 content in
2 2

methane in the scrubber water is negligible at the inlet the atmosphere, respectively) can be used as initial guesses. In this
(xCH ;L;in;SCR  0) and at equilibrium with the entering gas phase case, a particular procedure is required to ensure the numerical
0 4 1
convergence of the collocation method used in the bvp4c routine.
@xCH ;L;out;SCR ¼ H CH pG;in;SCR x
x CH4 ;G;in;SCR
A, Indeed, the profile of xCH4 ;L;SCR with respect to height is non-
4 4 RT CO2 ;G;in;SCR xCH4 ;G;in;SCR ð1xCO2 ;G;in;SCR xCH4 ;G;in;SCR Þ
qL MCO
þ M þ Minert
2 CH4
644 C.E. Wylock, W.M. Budzianowski / Chemical Engineering Science 170 (2017) 639–652

monotonic, contrary to the other variables. It results from the com-

petition between two opposite contributions to the mass transfer
driving force. On the one hand, the CH4 molar fraction in the gas
increases with column height, while the total gas pressure
decreases. On the other hand, the dissolved CH4 concentration in
the entering liquid is almost zero. There is thus a sharp variation
in the dissolved CH4 concentration at the liquid inlet, which may
disrupt the collocation method. This difficulty is overcome by a
continuation procedure on xCH4 ;L;in;SCR , which is gradually decreased,
from a value close to equilibrium with xCH4 ;G;out;SCR to its actual
value. The computed profiles being used as initial guesses for the
next iterations, this procedure is not used anymore after the first
one.
At the flash tank feeded by xCO2 ;L;in;FLS ¼ xCO2 ;L;out;SCR ,
xCH4 ;L;in;FLS ¼ xCH4 ;L;out;SCR and Q L;in;FLS ¼ Q L;out;SCR , Eqs. (21)–(26) are
solved with the routine fsolve to determine Q G;out;FLS , Q L;out;FLS ,
xCO2 ;G;out;FLS , xCO2 ;L;out;FLS , xCH4 ;G;out;FLS and xCH4 ;L;out;FLS
The liquid leaving the flash tank is conveyed to the stripper,
then xCO2 ;L;in;STR ¼ xCO2 ;L;out;FLS , xCH4 ;L;in;STR ¼ xCH4 ;L;out;FLS and
Q L;in;STR ¼ Q L;out;FLS . At the stripper gas inlet, Q G;in;STR is and the air
composition is known: xCO2 ;G;in;STR ¼ 4  104 and
7
xCH4 ;G;in;STR ¼ 2  10 . The evolution profiles of xCO2 ;G;STR , xCH4 ;G;STR ,
xCO2 ;L;STR , xCH4 ;L;STR , Q G;STR and Q L;STR along the height HSTR are com-
puted by solving Eqs. (14)–(17) with the bvp4c routine, enabling
the determination of the outlet variables xCO2 ;G;out;STR , xCH4 ;G;out;STR ,
xCO2 ;L;out;STR , xCH4 ;L;out;STR , Q G;out;STR and Q L;out;STR .

4. Results and discussion

4.1. Model validation

The scrubbing column model (i.e. mass transfer in a packed col-

umn) validated by using experimental results obtained by different
authors in order to minimise the risk of using incorrect or mislead-
ing data. They are presented in Table 2.
Fig. 2. Comparison of experimental data compiled in Table 2 with simulated results
Simulation results are compared to experimental data and aver- for various biogas upgrading plants: CO2 removal from biogas (a) and molar fraction
age deviations are calculated. Fig. 2-a compares CO2 removal from of CO2 in biomethane (b).

Table 2
Experimental data on collected in the literature for the scrubber model validation.

N° pG;in;SCR DSCR HSCR Q G;in;SCR Q L;in;SCR xCO2 ;G;in;SCR xCO2 ;G;out;SCR pFLS Ref.
(MPa) (m) (m) (m3/h) (kg/s) (MPa)
A1 1.0 0.15 3.0 20 1.00 0.40 0.070 – Nock et al. (2014), Läntelä and
A2 1.00 0.35 0.070 Luostarinen (2013)
A3 1.03 0.40 0.065
A4 1.03 0.35 0.065
A5 1.06 0.40 0.060
A6 1.06 0.35 0.060
A7 1.08 0.40 0.055
A8 1.08 0.35 0.055
A9 1.11 0.40 0.050
A10 1.11 0.35 0.050
A11 1.14 0.40 0.045
A12 1.14 0.35 0.045
A13 1.17 0.40 0.040
A14 1.17 0.35 0.040
A15 1.19 0.40 0.035
A16 1.19 0.35 0.035
A17 1.22 0.40 0.030
A18 1.22 0.35 0.030
B1 0.8 0.15 3.5 1.0 0.42 0.32 0.050 – Chandra et al. (2012)
B2 1.0 0.040
C1 0.3 0.10 1.0 0.3 0.3 0.40 0.108 – Huang et al. (2015)
D1 0.8 0.10 1.0 242.3 13.3 0.452 0.0047 0.3 Götz et al. (2011)
D2 12.06 0.0036 0.4
 C.E. Wylock, W.M. Budzianowski / Chemical Engineering Science 170 (2017) 639–652 645

biogas for a range of different biogas upgrading plants. The CO2

removal efficiency from biogas is defined as follows:
xCO2 ;G;in;SCR  xCO2 ;G;out;SCR
gCO2 ¼ 100% ð27Þ
xCO2 ;G;in;SCR
Fig. 2-b presents the comparison of experimental and simulated
molar fraction of CO2 in biomethane (xCO2 ;G;out;SCR ).
The data presented in Fig. 2-a show a small deviation for CO2
removal (1.7% in arithmetic average) and those presented in
Fig. 2-b show a limited deviation (14.7%) for CO2 molar fraction
in biomethane. According to the weak scatter observed in Fig. 2,
it may be concluded that the scrubber model predict rather well
the global behavior of real systems for their given experimental
conditions regarding to the CO2 separation.

4.2. Reference case

As a reference case, a plant is scaled with the following criteria:

a stream of 250 Nm3/h of raw biogas containing 35% molar of CO2
and 64% molar of CH4 has to be treated to reduce the CO2 content
down to 2% molar. The pressure is set to 8 bar at the scrubber inlet,
1.2 bar and at the stripper inlet and 1.1 bar in the flash tank. The
temperature is set to 288.15 K in all devices. As mentioned in Sec- Fig. 4. Post-computation liquid temperature evolution with height in the scrubber
tion 3.1, three parameters have to be defined in order to close the (a) and the stripper (b).
model equation system. These are related to the scrubbing water
regeneration and they can be viewed as regulation parameters.
The following values have been selected: xCO2 ;L;in;SCR ¼ 3:6  105 , The performance of the scaled plant are then evaluates. Using
xCO2 ;L;out;SCR ¼ 8  103 and xCO2 ;G;out;STR ¼ 0:27. The scaling leads to the identified values, it is found that the biogas treatment gener-
the following characteristics: DSCR ¼ 0:99 m, HSCR ¼ 5:26 m, ates 166 Nm3/h of biomethane. The flash tank efficiency is close
Q L;in;SCR ¼ 23:3 kg/s (81.28 m3/h), DSTR ¼ 0:99 m, HSTR ¼ 8:76 m to 99%, and the methane loss (at the stripper outlet) are about
and Q G;in;STR ¼ 8:3  102 kg/s (231 Nm3/h). 6102 Nm3/h.

Fig. 3. Evolution of xCO2 ;G , xCH4 ;G , xCO2 ;L and xCH4 ;L with the height in the scrubber (a) and in the stripper (b).
646 C.E. Wylock, W.M. Budzianowski / Chemical Engineering Science 170 (2017) 639–652

The evolution of the CO2 and CH4 mass fraction in the gas and in scrubber, this assumption is not rigorous but seems nevertheless
the liquid of the scrubber and the stripper can also be examined. reasonable. Moreover, this estimation considers an adiabatic
They are presented in Fig. 3. column, whereas in a real system there would be heat transfer
with the ambient air through the column walls. The actual temper-
4.3. Thermal effect evaluation ature deviation should be therefore smaller than the estimated
one.
Thanks to the mass transfer rate evaluated in the reference case,
the heat release associated with the CO2 absorption and its reac- 4.4. Influence of regulation parameters
tion with water can be estimated. It is realized to assess the
assumption validity of isothermal transfer. According to The effect of the three regulation parameters xCO2 ;L;in;SCR ,
Taghizadeh et al. (2001), the enthalpy of CO2 absorption in water xCO2 ;L;out;SCR and xCO2 ;G;out;STR are examined in order to assess their
is DEabs ¼ 20:3 kJ/mol. The enthalpy of reaction of CO2 with water influence on the scaling. Indeed, these parameters have to be
to form HCO 3 is evaluated to DEr ¼ 46 kJ/mol thanks to the selected appropriately since they may influence the column sizes
enthalpy of formation provided in Planck (1903). The CO2 chemical (determining the capital expenditure) and flows to ensure (deter-
conversion rate is deduced from the transfer rate by mining the operating expenditure) for the same imposed CO2
sCO2 ½HCO þ
3 L ½H L
þ . Considering an adiabatic column and neglecting abatement.
M CO
2
K 1 þ½HCO3 L þ½H L
Variations are then applied to xCO2 ;L;in;SCR , xCO2 ;L;out;SCR and
the heat transfer to the gas phase, the local liquid temperature
xCO2 ;G;out;STR to run simulations, keeping the target of 2% molar CO2
variation due to the heat of absorption and reaction is therefore
at the scrubber outlet. The results are examined in terms of varia-
calculated by:
! tions on DSCR , HSCR , Q L;in;SCR , DSTR , HSTR and Q G;in;STR , which are pre-
dT L sCO2 ½HCO3 L ½Hþ L sented in Figs. 3–5.
C p;L Q L ¼ DEabs þ DEr ð28Þ
dz MCO2 K 1 þ ½HCO3 L þ ½Hþ L It is shown in Fig. 5 that xCO2 ;L;in;SCR has a slight influence on the
requested HSTR (below 3% for 10% variations of xCO2 ;L;in;SCR ). For the
where C p;L is the liquid specific heat capacity. other ones, the influence can be considered negligible. Therefore,
The liquid temperature evolution with the height in the scrub- CO2 ;L;in;SCR is not a critical parameter, at least in the investigated
ber and the stripper are presented in Fig. 4. It is observed that the range, and it is low enough to ensure good performance of the
temperature deviation between inlet and outlet is 2.7 K in the scrubber.
scrubber and 0.7 K in the stripper. It seems therefore relevant to It is observed in Fig. 6 that the values of xCO2 ;L;out;SCR strongly
consider that the transfer is isothermal in the stripper. In the influence the requested scrubber height to maintain the same

Fig. 5. Variations of scrubber and stripper characteristics with variations of xCO2 ;L;in;SCR .

Fig. 6. Variations of scrubber and stripper characteristics with variations of xCO2 ;L;out;SCR .
 C.E. Wylock, W.M. Budzianowski / Chemical Engineering Science 170 (2017) 639–652
CO2 abatement performance, while it slightly affects the other
characteristics. The variations of Q G;in;STR reach about 1% for 10%
variations of xCO2 ;L;out;SCR . They are below 1% for DSCR , Q L;in;SCR , DSTR
and HSTR .
Fig. 7 shows the characteristics variations with xCO2 ;G;out;STR . It
is observed that it is significant for HSTR and Q G;in;STR , while it
has no influence on the scrubber characteristics. It shows that
decrease the targeted CO2 content in the air leaving the stripper
is interesting, in the investigated range, because it requires a
decrease of the stripper height but it is offset by the need of
increasing also the stripping air flow rate to keep constant the
CO2 abatement.
4.5. Influence of operating conditions
The sensitivity of the plant configuration with respect to the
operating parameters is investigated. Starting from the reference
case identified in 4.2, QL;in;SCR , QG;in;STR , Q G;RAW , xCO2 ;G;RAW , T, pG;in;SCR ,
pG;in;STR , pG;FLS are varied and their influence on the gas streams at
the scrubber and stripper outlet are computed. The performance
is evaluated on the basis of two criteria: the CO2 ratio at the scrub-
ber outlet xCO2 ;G;out;SCR and the methane loss at the stripper outlet
defined by kCH4 ;out;STR ¼ Q G;out;STR  yCH4 ;G;out;STR . They are presented
in relative variations in Figs. 8–15, respectively.
4.5.1. Scrubbing water flow rate
It appears from Fig. 8 that the scrubbing water flow rate Q L;in;SCR
has a considerable influence on the scrubbing performance. Indeed,
even small variations can affect significantly xCO2 ;G;out;SCR and
Fig. 7. Variations of scrubber and stripper characteristics with variations of xCO2 ;G;out;STR .
Fig. 8. Variations of CO2 ratio at the scrubber outlet and CH4 loss at the stripper outlet with variations of scrubbing water flow rate.
647
kCH4 ;out;STR . They respectively decrease and increase while Q L;in;SCR
increase, meaning that a high Q L;in;SCR is favorable for the CO2
scrubbing efficiency but it can be set off by an increase of the
methane loss. Q L;in;SCR is therefore an operating parameter that
has to be determined and controlled with accuracy in order to opti-
mize and to maintain the performance of the plant.
4.5.2. Stripping air flow rate
The stripping air flow rate Q G;in;STR appears to be also an impor-
tant parameter, according to Fig. 9. As it could be expected, when it
increases, the methane loss is slightly increased while xCO2 ;G;out;SCR is
decreased. It is therefore also a parameter to control but the sensi-
tivity of the system is weaker compared to the previous one.
4.5.3. Raw biogas flow rate and composition
Several external parameters may affect a digester during oper-
ation (temperature, feed composition . . .), therefore the character-
istics of the raw biogas to treat may variate more or less with time.
It is thus important to predict how it would affect the upgrading
plant performance in order to adapt the operating parameters for
keeping constant the performance. Fig. 10 presents influence of
the raw biogas flow rate Q G;RAW . It is observed that an increase of
Q G;RAW increases considerably xCO2 ;G;out;SCR in relative variation,
while it tends to decrease the methane loss. In such a situation,
an appropriate corrective action should be an increase of Q L;in;SCR .
In addition, if the Q G;RAW decreases, the scrubbing is more efficient
and then the treated biogas is richer in CH4. This tends to increase
the CH4 partial pressure, leading to an enhanced absorption in the
scrubbing water and inducing a higher methane loss. The raw bio-
648 C.E. Wylock, W.M. Budzianowski / Chemical Engineering Science 170 (2017) 639–652

Fig. 9. Variations of CO2 ratio at the scrubber outlet and CH4 loss at the stripper outlet with variations of stripping air flow rate.

Fig. 10. Variations of CO2 ratio at the scrubber outlet and CH4 loss at the stripper outlet with variations of raw biogas flow rate.

Fig. 11. Variations of CO2 ratio at the scrubber outlet and CH4 loss at the stripper outlet with variations of raw biogas CO2 fraction.

gas flow rate needs therefore to be monitored with accuracy in loss is also increased when the temperature decreases. It can
order to adapt efficiently the operating conditions. Similarly, if results from a combination of an increase of the CH4 absorption
the CO2 content of the raw biogas xCO2 ;G;RAW increases, the same in the scrubber (due to higher solubility and partial pressure)
trend is observed than for Q G;RAW , as it can be seen in Fig. 11. and a decrease of the its desorption in the flash tank.

4.5.4. Ambient temperature 4.5.5. Gas pressures

The temperature influence is investigated by varying the tem-
perature of all units (scrubber, stripper and flash). The results are
presented in Fig. 12. It is noticed that a slight temperature increase
may increase significantly the xCO2 ;G;out;SCR , due to the decrease of
the CO2 solubility in water. Besides, the trend is not so clear for
CH4, since its absorption depends also on the temperature and it
is coupled to the CO2 absorption. When the temperature increases,
the methane loss first decreases and after increases. The methane
According to Fig. 13, the influence of the gas pressure at the
scrubber inlet on xCO2 ;G;out;SCR meets the expectations: it decrease
as pG;in;SCR increases, thanks to the enhanced absorption in the
scrubber. An interesting trend is observed for kCH4 ;out;STR : it
decreases as pG;in;SCR increases. It is rather surprising since it would
be expected that increasing the scrubbing pressure enhance the
CH4 absorption in the scrubbing water and then the methane loss
at the stripper outlet. This results shows pG;in;SCR can also be used
 C.E. Wylock, W.M. Budzianowski / Chemical Engineering Science 170 (2017) 639–652 649

Fig. 12. Variations of CO2 ratio at the scrubber outlet and CH4 loss at the stripper outlet with variations of temperature.

Fig. 13. Variations of CO2 ratio at the scrubber outlet and CH4 loss at the stripper outlet with variations of scrubber inlet pressure.

Fig. 14. Variations of CO2 ratio at the scrubber outlet and CH4 loss at the stripper outlet with variations of stripper inlet pressure.

for corrective actions to maintain the plant performance when the
biogas characteristics are varying.
The trend is different for pG;in;STR , as it can be seen in Fig. 14.
When pG;in;STR is increased, xCO2 ;G;out;SCR is increased and kCH4 ;out;STR
is slightly decreased. It is therefore favorable to use the lowest pos-
sible pressure at the stripper, since high pressure hinders the CO2
desorption from the scrubbing water and therefore decrease the
treatment performance.
The opposite trend is observed for pG;FLS , as presented in Fig. 15,
with a more significant influence on kCH4 ;out;STR . This latter increases
if pG;FLS because it hinders the CH4 desorption by the flash opera-
tion. It is favorable to use the lowest possible pressure. However,
this tends also to increase xCO2 ;G;out;SCR , because more CO2 are rein-
jected in the scrubber. Therefore, pG;FLS has to be regulated in cou-
pling with other operating parameters like Q L;in;SCR and pG;in;SCR .
4.6. Influence of model parameters
In order to calibrate the proposed model with experimental
results, a particular attention should be paid to the accurate esti-
650 C.E. Wylock, W.M. Budzianowski / Chemical Engineering Science 170 (2017) 639–652

Fig. 15. Variations of CO2 ratio at the scrubber outlet and CH4 loss at the stripper outlet with variations of flash tank pressure.

mation of model parameters. On the one hand, the model is inher- umn independently. However, the need of accuracy is higher for
ently sensitive to the Henry coefficients (H CO2 and H CH4 ) and the the CO2 transfer coefficient than for the CH4 one. This need is also
gas-liquid transfer coefficients in both scrubber (aK L;CO2 ;SCR and higher for the scrubber than for the stripper. These trends are
aK L;CH4 ;SCR ) and stripper (aK L;CO2 ;STR and aK L;CH4 ;STR ). It can be shown quantified in Figs. 18–21. It is observed that the highest influence
that inaccuracy on any of these parameters may influence several
outlet variables. Their combined inaccuracies can therefore com-
plicate interpretation of experiments. For instance, they can skew
the study of the influence of a given regulation parameters by
enhancing or damping its effects. On the other hand, it is evaluated
that the model is rather insensitive to the reaction equilibrium
constant (K 1 ).
The sensitivity of the performance computed by the models
with respect to H CO2 and H CH4 are presented in Figs. 16 and 17,
respectively. The model predict a considerable influence of H CO2
both xCO2 ;G;out;SCR and kCH4 ;out;STR . As it could be expected, it is
observed in Fig. 16 increasing values of H CO2 decrease significantly
xCO2 ;G;out;SCR . However, it increases also kCH4 ;out;STR because the scrub-
bing water in the scrubber is in contact with a CH4 richer gas
stream. The effect of H CH4 is more moderate, as it can be seen in
Fig. 17. Increasing values of H CH4 increases obviously kCH4 ;out;STR
and increases also slightly xCO2 ;G;out;SCR .
The Henry coefficients can be estimated thanks to various cor-
relations available in the literature. It is nevertheless recom-
mended to assess the accuracy of these expressions, since it is Fig. 17. Variations of CO2 ratio at the scrubber outlet and CH4 loss at the stripper
shown that it can significantly affect the process performance. outlet with variations of the CH4 Henry coefficient H CH4 .
Concerning the transfer coefficient, it is recommended to esti-
mate the CO2 and CH4 gas-liquid transfer coefficient on each col-

Fig. 16. Variations of CO2 ratio at the scrubber outlet and CH4 loss at the stripper Fig. 18. Variations of CO2 ratio at the scrubber outlet and CH4 loss at the stripper
outlet with variations of the CO2 Henry coefficient H CO2 . outlet with variations of the CO2 transfer coefficient in the scrubber aK L;CO2 ;SCR .
 C.E. Wylock, W.M. Budzianowski / Chemical Engineering Science 170 (2017) 639–652
Fig. 19. Variations of CO2 ratio at the scrubber outlet and CH4 loss at the stripper
outlet with variations of the CH4 transfer coefficient in the scrubber aK L;CH4 ;SCR .
Fig. 20. Variations of CO2 ratio at the scrubber outlet and CH4 loss at the stripper
outlet with variations of the CO2 transfer coefficient in the stripper aK L;CO2 ;STR .
Fig. 21. Variations of CO2 ratio at the scrubber outlet and CH4 loss at the stripper
outlet with variations of the CH4 transfer coefficient in the stripper aK L;CH4 ;STR .
651
is for aK L;CO2 ;SCR . It can be seen in Fig. 18 that both xCO2 ;G;out;SCR and
kCH4 ;out;STR decrease when aK L;CO2 ;SCR . It means that maximize the
transfer efficiency of the scrubber has a considerable favorable
effect on the global performance of the plant. By contrast, the influ-
ence of aK L;CH4 ;SCR is slight. Surprisingly, it is observed in Fig. 19 that
kCH4 ;out;STR decreases slightly for increasing values of aK L;CH4 ;SCR ,
while there is no clear trend for xCO2 ;G;out;SCR . The influence of
aK L;CO2 ;STR is illustrated in Fig. 20. It is observed that increasing val-
ues of aK L;CO2 ;STR decrease xCO2 ;G;out;SCR . The maximization of the
transfer efficiency in the stripper has a significant considerable
favorable effect on the global performance, at least regarding to
the CO2 abatement. It is explained by the fact that a high transfer
coefficient in the stripper favors the CO2 depletion in the scrubbing
water, which thus enhances the CO2 transfer driving force in the
scrubber. However, it is also observed that it induces a slight
increase of kCH4 ;out;STR . Finally, it is observed in Fig. 21 that
aK L;CH4 ;STR has a very slight influence of kCH4 ;out;STR , which increases
for increasing values of aK L;CH4 ;STR and almost no influence on
xCO2 ;G;out;SCR .
These results shows therefore that experimental investigation
needs to focus on the CO2 and CH4 Henry coefficients and on the
CO2 gas-liquid transfer coefficient in the scrubber and in the
stripper.
5. Conclusions
In this work, a model of a scrubber-flash-stripper high pressure
water scrubbing process is implemented to estimate appropriate
device size for reaching a given performance as well as to compute
the performance of a given plant.
The scrubbing part of the model (i.e. gas-liquid absorption in
a packed column) has been validated by means of comparison
with experimental data available in the literature. The validated
model is used to scale a reference biogas upgrading plant. The
sensitivity of the scaling with respect to parameters related to
the scrubbing water recycling is made (Section 4.4). It appears
that the CO2 mass fraction in the inlet scrubbing water (CO2
lean) mostly influences the requested stripper height, which
decreases as this mass fraction increases. Similarly, the requested
scrubber height increases with the CO2 mass fraction targeted in
the water leaving the scrubber (CO2 rich). Finally, the selected
CO2 mass fraction in the stripping air leaving the stripper influ-
ences the stripper height and the stripping air flow rate. They
respectively increase and decrease when this mass fraction is
increased.
The sensitivity of the plant configuration with respect to the
operating parameters is also investigated and presented in Sec-
tion 4.5. The plant performances are evaluated by the CO2 ratio
at the scrubber outlet and the methane loss at the stripper outlet.
It appears that the scrubbing water flow rate, the flow rate and CO2
fraction of the raw biogas, the ambient temperature and the pres-
sure in the flash tank have a considerable influence, while the
stripping air flow rate and the scrubber and stripper inlet pressures
have a moderate influence. The results are useful to predict the
effect of biogas characteristics variations for the plant regulation.
By integrating such a model in a control system, the computed
appropriate corrective actions should maintain the upgrading
plant performance.
Moreover, the sensitivity of the model with respect to its impor-
tant parameters – the solubility and transfer coefficients – is ana-
lyzed, in order to gain insight on the parameter to focus in the
framework of a model calibration by experimental results. The
analysis shows that experimental investigation needs to focus on
the CO2 and CH4 Henry coefficients and on the CO2 gas-liquid
transfer coefficient in the scrubber and in the stripper.
652 C.E. Wylock, W.M. Budzianowski / Chemical Engineering Science 170 (2017) 639–652
A first improvement of the current model would be realized by
including the temperature dependence of the physico-chemical
parameters at the local scale and by taking into account the water
evaporation/condensation in the mass transfer equations. A deeper
improvement would be provided by integrating a more realistic
description of the hydrodynamic in the columns, for instance by
coupling the Matlab code with a 2-D dimensional model of the col-
umn considered as porous medium thanks to the COMSOL Multi-
physics software. Similarly, it would be advantageous to take
into account the non-equilibrium effect in the flash tank modelling.
Indeed, it is considered in this work as instantaneously at equilib-
rium, eliminating its volume in equations. Such an improved
model would enable an accurate estimation of the required
volume.
Acknowledgments
The support obtained from the members of the Renewable
Energy and Sustainable Development (RESD) Group (Poland) under
the grant no. RESD-RDG04/2016 is greatly acknowledged.
References
Abatzoglou, N., Boivin, S., 2009. A review of biogas purification processes. Biofuels
Bioprod. Biorefin. 3, 42–71.
Beil, M., Beyrich, W., 2013. Biogas upgrading to biomethane. In: Wellinger, A.,
Murphy, J., Baxter, D. (Eds.), The Biogas Handbook. Woodhead Publishing, pp.
342–377.
Billet, R., Schultes, M., 1993. Predicting mass transfer in packed columns. Chem. Eng.
Technol. 77, 1–9.
Budzianowski, W.M., 2012. Benefits of biogas upgrading to biomethane by high-
pressure reactive solvent scrubbing. Biofuels Bioprod. Biorefin. 6 (1), 12–20.
Budzianowski, W.M., Kozioł, A., 2006. Stripping of ammonia from aqueous solutions
in the presence of carbon dioxide. Effect of negative enhancement of mass
transfer. Chem. Eng. Res. Des. 83 (A2), 196–204.
Budzianowski, W.M., Wylock, C.E., Marciniak, P.A., 2017. Power requirements of
biogas upgrading by water scrubbing and biomethane compression:
comparative analysis of various plant configurations. Energy Convers. Manage.
Cents, A.H.G., Brilman, D.W.F., Versteeg, G.F., 2005. CO2 absorption in carbonate/
bicarbonate solutions: the Danckwerts-criterion revisited. Chem. Eng. Sci. 60,
5830–5835.
Chandra, R., Vijay, V., Subbarao, P., 2012. Vehicular quality biomethane production
from biogas by using an automated water scrubbing system. ISRN Renew.
Energy. no. 2012:904167.
Coulson, J.M., Richardson, J.F., 1999. . Chemical Engineering, 6 ed., vol. 1.
Butterworth Heinemann.
Cowie, Watt, 1971. Diffusion of methane and chloromethanes in air. Can. J. Chem.
49, 74.
Danckwerts, P.V., 1970. Gas-Liquid Reactions. McGraw-Hill.
Danckwerts, P., Sharma, M., 1966. Absorption of carbon dioxide into solutions of
alkalis and amines. Chem. Eng., 244–280
Edwards, T.J., Maurer, G., Newman, J., Prausnitz, J.M., 1978. Vapor-liquid equilibria
in multicomponent aqueous solutions of volatile weak electrolytes. A.I.Ch.E. J.
24, 966–976.
Götz, M., Köppel, W., Reimert, R., Graf, F., 2011. Optimierungspotenzial von
Wäschen zur Biogasaufbereitung. Teil 1-Physikalische Wäschen. Chem. Ing.
Tech. 83 (6), 858–866.
Guo, H., Chen, Y., Lu, W., Li, L., Wang, M., 2013. In situ Raman spectroscopic study of
diffusion coefficients of methane in liquid water under high pressure and wide
temperatures. Fluid Phase Equilibria 60, 274–278.
Huang, L., Qing, C., Tao, H., Wang, Y., Liu, X., 2015. Experimental study for biogas
upgrading by water scrubbing under low pressure. Open Chem. Eng. J. 9, 34–38.
Läntelä, J., Luostarinen, J., 2013. D5.4 Results of design, construction and testing of
lowcost modular biogas upgrading systems. Deliverable of EU FP7VALORGAS
project.
Nock, W., Walker, M., Kapoor, R., Heaven, S., 2014. Modeling the water scrubbing
process and energy requirements for CO2 capture to upgrade biogas to
biomethane. Ind. Eng. Chem. Res. 53 (32), 12783–12792.
Onda, K., Takeuchi, H., Okumoto, Y., 1968. Mass transfer coefficients between gas
and liquid phases in packed columns. J. Chem. Eng. Jpn.
Planck, M., 1903. Treatise on Thermodynamics. Longmans, Green, London.
Reid, R.C., Prausnitz, J.M., Poling, B.E., 1986. The Properties of Gases and Liquids.
MacGraw-Hill, New York.
Ryckebosch, E., Drouillon, M., Vervaeren, H., 2011. Techniques for transformation of
biogas to biomethane. Biomass Bioenergy 35, 1633–1645.
Sander, P., 1999. Compilation of Henry’s Law constants for inorganic and organic
species of potential importance in environmental chemistry. Available: http://
www.mpch-mainz.mpg.d/~sander/res/henry.html.
Sun, Q., Li, H., Yan, J., Liu, L., Yu, Z., Yu, X., 2015. Selection of appropriate biogas
upgrading technology - a review of biogas cleaning, upgrading and utilisation.
Renew. Sustain. Energy Rev. 51, 521–532.
Taghizadeh, M., Jallut, C., Tayakout-Fayolle, M., Lieto, J., 2001. Non-isothermal gas–
liquid absorption with chemical reaction studies: temperature measurements
of a spherical laminar film surface and comparison with a model for the CO2/
NaOH system. Chem. Eng. J. 82 (1–3), 143–148.
Thrän, D., Billig, E., Persson, T., Svensson, M., Daniel-Gromke, J., Ponitka, J., Seiffert,
M., Baldwin, J., Kranzl, L., 2016. Biomethane - status and factors affecting
market development and trade. In: IEA Task 40 and Task 37 Joint Study.
Trambouze, P., Euzen, J.-P., 2002. Chemical Reactors: From Design to Operation.
Editions Technip, Paris.
Tsonopoulos, C., 1976. Ionization constants of water pollutants. J. Chem. Eng. Data
21, 190–193.
Vas Bhat, R., Kuipers, J., Versteeg, G., 2000. Mass transfer with complex chemical
reactions in gas-liquid systems: two-step reversible reactions with unit
stoichiometric and kinetic orders. Chem. Eng. J. 76 (2), 127–152.
Versteeg, G.F., Van Swaaij, W.P.M., 1988. Solubility and diffusivity of acid cases
(CO2, N2O) in aqueous alkanolamine solutions. J. Chem. Eng. Data 33, 29–34.
Whitman, W.G., 1923. The two-film theory of absorption. Chem. Metal. Eng. 29 (4),
146–148.
Wylock, C., Dehaeck, S., Cartage, T., Colinet, P., Haut, B., 2011. Experimental study of
gas-liquid mass transfer coupled with chemical reactions by digital holographic
interferometry. Chem. Eng. Sci. 66, 3400–3412.
Wylock, C., Antuñano, N., Arias, P.L., Haut, B., 2014. Analysis of the simultaneous
gas-liquid CO2 absorption and liquid-gas NH3 desorption in a
hydrometallurgical Waelz oxides purification process. Int. J. Chem. Reactor
Eng. 12, 1–14.