Small-Scale Biogas High Pressure Water Upgrading

KTH Industrial Engineering
and Management
Small-Scale Biogas Upgrading System Modeling Tool

Development
David Saldarriaga
Master of Science Thesis

KTH School of Industrial Engineering and Management
Department of Energy Technology
EGI-2013-MJ232X
Unit of Heat and Power
SE-100 44 Stockholm
2018
MASTER THESIS: Small-Scale Biogas Upgrading System Modeling Tool Development
KTH – Royal Institute of Technology

Department of Energy Technology 2 of 111
Master of Science Thesis TRITA-ITM-EX 2018:625
Small-Scale Biogas Upgrading System Modeling Tool

Development
David Saldarriaga
Approved Examiner Supervisor
2018-September-26 Anders Malmquist Anders Malmquist
Commissioner Contact person
Abstract
The potential of biogas to decarbonize society depends partially on the success of small-scale systems.
Two specific locations where biogas units can be implemented are considered in this study: small
farms and small isolated populations. The access to energy sources, either traditional or renewable
for these is often restricted and typically costly. Clean raw biogas can be the energy source to satisfy
power generation, cooking, and heating needs. Upgrading widens the options to transport fuel and
energy storage helping positively in the unlinking between production and demand.
Water upgrading has three essential and exclusive benefits that make it a highly feasible solution for
these isolated locations or small agricultural units. It is in general available in these places; it has a
very low environmental impact if leakage or malfunctioning of the system, and has no toxicity per se.
To aid the development of the biogas industry focused on small-scale systems a fast, easy to use, low
cost, customizable tool is needed to help the design process of the high-pressure water upgrading
units. The present study covers the development of such a tool. In the present report, the basis of the
model to solve the mass balance of the system and to calculate the dimensions of the scrubber are
described. The scrubber model is an implementation of the NTU-HTU model proposed by Billet and
Schultes in two major publications (Billet, 1995) and (Billet & Schultes, 1999). The strategies used
to solve the set of closed loop equations, and iterations are presented in a block diagram fashion. The
tool was developed in visual basic for applications using Excel as the hosting application.
The results of the tool are compared against those obtained from the same model ran in Aspen Plus.
To perform such a comparison, 540 cases were used. The cases are the result of running three nominal
raw biogas flows, using three different packing materials, varying the raw biogas and water flows,
varying pressure, temperature, and height of the scrubber, and varying the pressure of the flash tank.
Three sensitivity analyses are performed to check the influence of some variables in the model. One
is designed to check the influence of the exponent choice for dimensionless numbers in the calculation
of the volumetric mass transfer coefficient as an example of the various points where the Billet model

is adjusted to follow the behavior of packed columns. Another analysis consists of comparing the
results of height using different packing materials to see how the six packing constants affect the
results of the calculations. The third analysis is performed to check the influence of the methane
absorption model where three different approaches were used.
The results show that the tool behaves coherently, and a validation step can be implemented via real
experimental tests comparison. The tool has several points where adjustments can be made, like the
mentioned exponents for the dimensionless numbers, or the constants used in the interfacial area
calculation and the correction of the 𝐶𝑆 and 𝐶𝐹𝑙 packing constants when inversion point has been
reached.
The implementation of high-pressure water scrubbing together with a flash tank can achieve slip
values as low as 0.25% or even lower. The lower the slip, the higher the energy needed to upgrade is.
Thus, there is a trade-off between slip and internal energy demand.

Sammanfattning
Potentialen hos biogas för att minska samhällets kolberoende är delvis beroende avframgången för
småskaliga system. I denna studie betraktas två specifika platser där biogasenheter kan användas:
små lantbruk och små isolerade byar. Tillgången till energikällor, såväl traditionella som förnybara,
är ofta begränsad och är vanligtvis dyr för dessa platser. Renad biogas kan bli enenergikällan för att
tillgodose kraftproduktion, matlagning och uppvärmning. Biogasuppgradering breddar
användningsalternativen till användning som drivmedel och till energilagring, vilket bidrar på ett
positivt sätt till koppla isär energiproduktion och energiförbrukning.
En vattenskrubber har tre viktiga och unika fördelar som gör den en väldig användbar lösning för
dessa isolerade platser eller för små jordbruksenheter. Vanligtvis är vatten tillgängligt på dessa
platser, det har en synnerligen låg miljöpåverkan om det blir läckor eller funktionsfel i systemet och
det är icke-giftigt.
För att stödja utvecklingen av biogasindustrin med inriktning på småskaliga system behövs ett snabbt,
lättanvänt, billigt och anpassningsbart verktyg för att genomföra design en högtrycks vattenskrubber.
Den här studien omfattar utvecklingen av ett sådant verktyg. I föreliggande rapport beskrivs grunden
för modellen för att lösa systemets massbalans och att beräkna och dimensionera skrubbern.
Skrubber-modellen innehåller en implementering av NTU-HTU-modellen som Billet och Schultes
föreslagit i två stora publikationer (Billet, 1995) och (Billet & Schultes, 1999). De strategier som
används för att lösa uppsättningen av slutna loop-ekvationer och iterationer presenteras i ett
blockdiagram. Verktyget har utvecklats i VBA (Visual Basic for Applications) och använder Excel
som programvarumiljö.
Resultaten som erhålls med det utvecklade verktyget jämförs med de som erhålls från samma modell
i Aspen Plus. För att utföra en sådan jämförelse användes 540 testfall. Fallen är resultatet av
modelleringen av tre nominella biogasflöden, där tre olika typer av fyllmaterial/fyllkroppar används.
För varje testfall varieras rå biogas, vattenflöde, tryck, temperatur och höjd av vattenskrubbern, samt
trycket i flash-tanken.
Tre känslighetsanalyser utförs för att kontrollera påverkan av vissa variabler i modellen. Den första
är utförmad för att kontrollera exponeringsvalets inverkan på dimensionslösa tal vid beräkningen av
den volymetriska massöverföringskoefficienten, som ett exempel av flera punkter där Billets modell
är justerad för att följa vattenskrubbers beteendet. Den andra analysen består av att jämfora
skrubberns beräknade höjd när olika fyllmaterial används för att evaluera hur påverkar de sex
fyllmaterial konstanterna resultaten av beräkningar. Och den tredje analysen utförs för att kontrollera
påverkan av metans absorptionsmodell när tre olika metoder användes.
Resultaten visar att verktyget uppträds på ett koherent sätt och ett valideringssteg kan baserat på detta
genomföras med verkliga experimentella jämförelser. Verktyget har flera delar där justeringar kan
göras, som t.ex. exponenterna för dimensionslösa tal och konstanterna som används i interface-
beräkningarna, samt korrigeringen av 𝐶𝑆 och 𝐶𝐹𝑙 konstanter när punkten av inversion har uppnåtts.
Implementeringen av högtrycks vattenskrubbers tillsammans med en flash-tank kan medföra en slipp
(förklaras senare i rapporten) så låg som 0,25% eller ännu lägre. Ju lägre slipp är desto högre är
energin som behövs för att uppgradera biogasen. Det finns således en avvägning mellan slipp och
intern energiförbrukning.


Contents
Abstract ...................................................................................................................................................................... 3
Sammanfattning ......................................................................................................................................................... 5
Abbreviations and Symbols .......................................................................................................................................10
List of Figures.............................................................................................................................................................14
List of Tables ..............................................................................................................................................................17
1 Proposal ............................................................................................................................................................18
1.1 Background ..................................................................................................................................................... 18
1.2 Problem Formulation....................................................................................................................................... 23
1.3 Objective.......................................................................................................................................................... 24
1.4 Methodology ................................................................................................................................................... 24
1.5 Implementation ............................................................................................................................................... 25
1.6 Problems and Limitations ................................................................................................................................ 25
1.7 Expected Outcomes ......................................................................................................................................... 26
2 Upgrading Techniques .......................................................................................................................................27

2.1 Physicochemical Upgrading Systems .............................................................................................................. 27
2.1.1 Absorption .................................................................................................................................................. 27
2.1.1.1 Agitated Vessels ................................................................................................................................. 27
2.1.1.2 Bubble-plate Towers .......................................................................................................................... 28
2.1.1.3 Spray Towers ...................................................................................................................................... 28
2.1.1.4 Wet scrubbers – Packed Towers ........................................................................................................ 28
2.1.2 Adsorption .................................................................................................................................................. 30
2.1.2.1 Pressure Swing Adsorption (PSA) ....................................................................................................... 31
2.1.3 Membrane Permeation............................................................................................................................... 32
2.1.4 Cryogenic Distillation .................................................................................................................................. 33
2.1.5 Biosling ........................................................................................................................................................ 33
2.2 Biological Upgrading Systems ......................................................................................................................... 34
2.2.1 Photosynthetic Upgrading .......................................................................................................................... 34
2.2.2 Hydrogenotrophic CO2 Reduction to CH4 ................................................................................................... 34
2.2.3 Biotrickling Filtration Upgrading (Deublein & Steinhauser, 2011) .............................................................. 35
2.3 Upgrading Technology Comparison ................................................................................................................ 36
2.4 Advantages and Disadvantages of Upgrading Techniques ............................................................................. 38
3 Water Scrubbing Columns .................................................................................................................................41

3.1 Mass transfer in columns ................................................................................................................................ 41
3.1.1 Operating line ............................................................................................................................................. 41
3.1.2 Equilibrium curve ........................................................................................................................................ 43
3.2 Column Operation - Fluid Dynamic Description .............................................................................................. 46
3.2.1 Loading and Flooding Points ....................................................................................................................... 47

3.2.1.1 Loading Point ..................................................................................................................................... 49

3.2.1.2 Flooding Point .................................................................................................................................... 50
3.2.2 Description of the Operating Intervals ....................................................................................................... 51
3.2.3 Column’s Diameter Selection ...................................................................................................................... 52
3.3 HTU-NTU Method ............................................................................................................................................ 53
3.3.1 HTU-NTU General Description .................................................................................................................... 53
3.3.2 HTU calculation ........................................................................................................................................... 56
3.3.3 NTU calculation ........................................................................................................................................... 59
3.3.4 Height Calculation Remark ......................................................................................................................... 60
3.4 Fluid Properties Calculation ............................................................................................................................. 61
3.4.1 Dynamic Viscosity ....................................................................................................................................... 61
3.4.2 Density ........................................................................................................................................................ 61
3.4.3 Diffusivity .................................................................................................................................................... 63
3.4.4 Surface Tension ........................................................................................................................................... 63
3.4.5 Solubility ..................................................................................................................................................... 64
4 Upgrading Cycle Calculation ..............................................................................................................................65

4.1 Mass Balances ................................................................................................................................................. 66
4.2 CH4 Absorption Model ..................................................................................................................................... 67
4.3 Flash Tank Model ............................................................................................................................................ 69
4.4 Closed Loop Equation Solving Strategy ........................................................................................................... 70
5 Internal Energy Consumption ............................................................................................................................72

5.1 Compressor...................................................................................................................................................... 72
5.2 Coolers ............................................................................................................................................................. 73
5.3 Water Pump and Air Blower ............................................................................................................................ 74
5.4 Electricity Generator........................................................................................................................................ 75
6 Model Implementation in VBA ..........................................................................................................................76

6.1 General Description of the Tool ....................................................................................................................... 76
6.2 User Interface .................................................................................................................................................. 76
6.3 Modeling Strategy ........................................................................................................................................... 77
7 Model Comparison ............................................................................................................................................82

7.1 General Framework for the Comparison ......................................................................................................... 82
7.2 Aspen Model: Block and Streams Description ................................................................................................. 83
7.3 Comparison Results ......................................................................................................................................... 85
7.3.1 Slip Comparison .......................................................................................................................................... 85
7.3.2 Concentration Comparison ......................................................................................................................... 88
7.3.3 Height of the scrubber calculation comparison .......................................................................................... 89
8 Sensitivity Analysis ............................................................................................................................................91

8.1 Sensitivity Analysis for the Cycle-Loop Model ................................................................................................. 91
8.2 Scrubber Model Sensitivity Analysis ................................................................................................................ 94

8.2.1 Dimensionless Exponent Changes in the Volumetric Mass Transfer Coefficient ....................................... 94
8.2.2 Packing Constants Change .......................................................................................................................... 95
9 Discussion .........................................................................................................................................................97
10 Sustainability Analysis .....................................................................................................................................101
11 Conclusions and Further Work ........................................................................................................................106

11.1 Conclusions .................................................................................................................................................... 106
11.2 Proposed Further Work ................................................................................................................................. 106
References ...............................................................................................................................................................108

Abbreviations and Symbols

Abbreviations
AD Anaerobic digester, anaerobic digestion

CBG Compressed biogas used as vehicle fuel
CHP Combined Heat and Power
CH4 Methane
CM Combined CH4 absorption model
CNG Compressed natural gas used as vehicle fuel
CO2 Carbon dioxide
DEA Diethanolamine
EQ Equilibrium CH4 absorption model
FE Flash equilibrium CH4 absorption model
GHG Greenhouse gases
HTU-NTU Height of the transfer unit – Number of transfer units
H2S Hydrogen sulfide
LBG Liquefied biogas
LHV Lower Heating Value
LNG Liquefied natural gas
LPSA Low-pressure swing adsorption
MEA Monoethanolamine
NH3 Ammonia
3
Nm Normal cubic meters. Normal refers to the volume of gas measured at 1.01325 bar and
273.15 K. (1 atm and 0°C)
N2 Nitrogen
O2 Oxygen
PSA Pressure swing adsorption. Also: Pressure swing absorption
RB Raw Biogas
UK United Kingdom
VBA Visual Basic for Applications (Microsoft)
VOC Volatile organic compound
Variable Names
𝐴 Cross section area of the absorption column. Also: variable used in the Peng-Robinson equation
of state
𝑎 Total packed surface area per packed volume. Also: variable used in the Peng-Robinson
equation of state. Also: variable used in the flash tank solving equations
𝐵 Variable used in the Peng-Robinson equation of state

𝑏 Variable used in the Peng-Robinson equation of state. Also: variable used in the flash tank
solving equations
𝑎ℎ Hydraulic area
𝑐 Molarity concentration. Also: variable used in the flash tank solving equations
𝐶𝐹 Inter-stage compression factor
𝐶𝐹𝑙 Packing constant used to calculate the flow resistance 𝜉𝐹𝑙
𝐶𝐿 Packing constant used to calculate the volumetric mass transfer coefficient
𝑐𝑝 Specific heat at constant pressure
𝑐𝑣 Specific heat at constant volume
𝐶𝑆 Packing constant used to calculate the flow resistance 𝜉𝑆
𝐷𝑥 Diffusivity coefficient for phase 𝑥.
𝑑 Diameter of the absorption column
𝑑𝑥 Diameter of the absorption column for the loading or flooding point
𝑑ℎ Hydraulic diameter
𝑓𝑦 CH4 absorption flow factor used for the internal flow of the scrubber
𝑓𝑘 Wall factor
𝐹𝑟 Froude number
𝐻 Total height of the absorption column
𝑖 or 𝑗 In an iteration an “i” case. Also: the “i” component in a summation
ℎ𝑙 Liquid holdup of the absorption column
𝐾 Temperature-dependent Henry’s constant
𝑘𝑖𝑗 Binary interaction parameter used in the Peng-Robinson equation of state
𝐿 Liquid. Also: Aqueous flow
𝑀 Molecular weight
𝑁 Molar flow correspondent to mass transfer between phases
𝑛 Number of compression stages. Also: Total components of a mixture
𝑚 Mass
𝑚𝑦𝑥 Slope of the equilibrium curve
𝑃 Power
𝑝 Pressure
𝑅 Universal gas constant
𝑅𝐵 Raw biogas flow
𝑅𝑒 Reynolds number
𝑇 Temperature
𝑆𝑐 Schmidt number
𝑠𝑓 Slip as a fraction
𝑠𝑙𝑖𝑝 Slip as molar flow

𝑢 Velocity or load
𝑢
̅̅̅𝐿 Local liquid velocity
̅𝑢̅̅𝑉̅ Average effective vapor velocity
𝑉 Vapor flows
𝑣̅ Specific volume
𝑋 Aqueous. Also: Liquid molar load
𝑥 Vapor mole fraction
𝑌 Vapor molar load
𝑦 Vapor mole fraction
Sub-indices
𝑎 Species “a”. Also: Absorption column

𝑎𝑖𝑟 Air
𝑎𝑑 Additional temperature
𝑎𝑡𝑚 Atmospheric. Also: Ambient conditions
𝑏 Bulk
𝑏𝑔 Biogas
𝐵 Base. Also: Blower
𝑐 Critical value
𝐶 Compressor
𝐶𝑂 Cooler
𝑑𝑒𝑣 Deviation
𝑒 Equilibrium
𝑓 Flash tank
𝐹𝑙 Flooding point
𝑖 Interphase
𝑖 or 𝑗 In an iteration an “i” case. Also: the “i” component in a summation
𝐿 Liquid phase or related to the wet surface of the packing
𝑘 Related to the wall factor 𝑓𝑘
𝑚 Mixture
𝑚𝑎𝑠 Mass
𝑚𝑒𝑐 Mechanical
𝑚𝑜𝑙 Mol. Also: Molar
𝑁𝑣𝑜𝑙 Normalized volume. Normal refers to the volume of gas measured at 1.01325 bar and 273.15 K.
(1 atm and 0°C)
𝑃 Pump
𝑜 Top of the column
𝑜𝑝 Operative. Also: Operational

𝑜𝑇 Overtemperature
𝑂𝑉 Overall
𝑜𝑣 Overpressure. Also: Overtemperature
𝑟 Reduced value
𝑆 Loading point. Also: Stripper
𝑆0 Thickness of the liquid film
𝑇 Temperature-dependent
𝑢 Bottom of the column
𝑉 Vapor phase
𝑣̅ Specific volume used in the Peng-Robinson equation of state
𝑣𝑜𝑙 Volume
𝑥 Loading point or Flooding point. Also: Liquid or Vapor. Also: “x” Compressor stage
2 Refers to CO2 as species
4 Refers to CH4 as species
Greek letters
𝛼 Variable used in the calculation of the Peng-Robinson equation of state

𝛽 Mass-transfer coefficient
𝛽 ∙ 𝑎𝑝ℎ Volumetric mass transfer coefficient
Δ Delta or change
𝜀 Void fraction
𝜂 Dynamic viscosity. Also: Efficiency
𝜉 Resistance factor
𝜌 Density
𝜎 Surface tension
𝜏 Time
𝜑 Variable used in the Peng-Robinson equation of state
𝜔 Acentric value

List of Figures
Figure 1 Number of industrial AD plants commissioned each year in the world from 1981 to 2016. In
total, there is one plant that lacks an upgrading system and another one that performs only
partial upgrading. (IEA Bioenergy, 2017) ....................................................................................... 18
Figure 2 Total Number of upgrading plants per country until 2016 (IEA Bioenergy, 2017)............................ 19
Figure 3 Added capacity year by year from 1981 to 2016. The red curve depicts the total cumulative
capacity in Nm3/h. .......................................................................................................................... 20
Figure 4 Plant type and size in Nm3/h distribution until 2016 (IEA Bioenergy, 2017). ................................... 21
Figure 5 Left: Total capacity technology distribution mix in 2016. Right: Sizes 0 – 100 Nm3/h range
technology capacity mix (IEA Bioenergy, 2017). ............................................................................ 21
Figure 6 Biogas paths. The amount of biogas used in each path is dependent on several factors. The
flow into upgrading is, thus, variable............................................................................................. 23
Figure 7 Left: Bubble plate tower. Right: Picture of a tray with bubble caps for a distillation column.
Figure adapted and picture obtained from (Sölken, 2018). .......................................................... 28
Figure 8 Water scrubber process. Adapted from (Wellinger, et al., 2013) and (Bauer, et al., 2013). ............ 29
Figure 9 Different industrial packing materials. 1 Cylindrical ring. 2 Berl-Saddle. 3 Novalox® Saddle. 4
Pall® ring (metallic). 5 Pall® ring (plastic). 6 Interpack®. 7 VSP®. 8 Igel®. 9 Novalox® - M. 10
VFF.Power-Pack®. Images obtained from (Vereinigte Füllkörper-Fabriken GmbH & Co. KG,
2016) .............................................................................................................................................. 30
Figure 10 Structured packing. Images obtained from (Raschig Gmbh, 2018)................................................. 30
Figure 11 PSA plant configuration. Four columns continuous process. Image adapted from (Wellinger,
et al., 2013). ................................................................................................................................... 31
Figure 12 Different membrane upgrading configurations. Image adapted from (Hoyer, et al., 2016). ......... 32
Figure 13 Gas - Liquid membrane technique. ................................................................................................. 33
Figure 14 Biosling process scheme. Figure obtained from (Biosling AB, 2012) .............................................. 34
Figure 15 AD process description (Sofer & Zaborsky, 1981). .......................................................................... 35
Figure 16 Scrubbing process. Left: Packed column. Center: Equilibrium and operating curves given in
molar load units. Right: Equilibrium and operating curves given in molar fraction units.
Figures adapted from (Billet, 1995). .............................................................................................. 41
Figure 17 Validation of constants fitted to laboratory data. In light blue the results of this study in black
original data. The original plot was extracted from (Carroll, et al., 1991). .................................... 44
Figure 18 Left: Liquid holdup and phase distribution for a low liquid load. Center: High liquid load. Right:
Schematic representation of packing and phase interaction. The right figure was adapted
from (Billet, 1995) .......................................................................................................................... 47
Figure 19 Loading and flooding points. Figure adapted from (Billet, 1995).................................................... 48
Figure 20 Section of the scrubbing column. The flow of CH4 𝑽 and H2O 𝑳 constant. ..................................... 53

Figure 21 Penetration model - Higbie Model. The time t of residence of the liquid packet is the time
needed to flow through a bubble of diameter d. The concentration n the liquid is cL and in
the vapor phase cV. ........................................................................................................................ 54
Figure 22 Example of the height calculation while varying the composition of the upgraded biogas.
Notice the non-linearity of the function. ....................................................................................... 60
Figure 23 High-pressure water upgrading cycle with a flash tank and stripper.............................................. 65
Figure 24. Simplified process omitting the stripper. ....................................................................................... 66
Figure 25 Qualitative description of the CH4 mass transfer behavior as a function of the height of the
column. Source Author of the present study................................................................................. 68
Figure 26 Left: Equilibrium concentration. Right: Flash equilibrium CH4 concentration. ............................... 68
Figure 27 High-pressure water upgrading cycle with auxiliary equipment highlighted.................................. 72
Figure 28 User Interface of the modeling tool developed. The interface has additional fields not shown
in the figure. The additional fields are where the packing material is selected, and the results
of the scrubber are displayed like the velocities of the vapor and liquid phases, the slope of
the equilibrium curve, the liquid holdup, the loading and flooding point loads among others.
........................................................................................................................................................ 77
Figure 29 Modeling tool general block flow .................................................................................................... 78
Figure 30 Loop block calculation strategy. ...................................................................................................... 78
Figure 31 Calculation strategy to solve for the height of the scrubber........................................................... 80
Figure 32 Slicing of the column. Strategy for applying HTU-NTU method. Qualitative description of the
density of the vapor phase behavior in the column as a function of the height. .......................... 81
Figure 33 Block layout of the Aspen model. (Aspen Technology, Inc, 2017) .................................................. 84
Figure 34 General comparison results of the slip calculations. Left: Whole range. Right: Detail between
3% and 9% of slip ........................................................................................................................... 86
Figure 35 Slip deviation graphical representation. Left: All the data plotted. Right: Zoom to data up to
1% slip. ........................................................................................................................................... 86
Figure 36 Histograms for Slip deviation comparison. For the scrubber model, 7 points were omitted in
the histogram since they are outliers that distort the histogram shape in the central focal
area. ............................................................................................................................................... 87
Figure 37 Concentration calculation deviation graphical representation. All the data plotted. .................... 88
Figure 38 Histograms for concentration calculation deviations comparison.................................................. 89
Figure 39 Results comparison for the calculated height of the column. ........................................................ 89
Figure 40 Histograms for the height deviations. ............................................................................................. 90
Figure 41 Average and Standard deviations for the calculations considering only the scrubber -No flash
tank- ............................................................................................................................................... 92
Figure 42 Average and Standard deviations for the calculations considering scrubber and flash tank. ........ 92
Figure 43 Sensitivity analysis. Calculated slip solving for yo4 on the Scrubber model. FE, CM and EQ
absorption models. ........................................................................................................................ 93

Figure 44 Sensitivity analysis. Calculated slip solving for yo4 on the Cycle model (Scrubber + Flash). FE,
CM and EQ absorption models. Left: All the data plotted. Right: Slip Detail from 0.025 to
0.5%................................................................................................................................................ 94
Figure 45 Height comparison between the results obtained using tool with the original Billet exponents
of 3/4 and 1/2 and those obtained with the tool using 1/2 exponent. ......................................... 95
Figure 46. Height comparison between the results obtained using tool with Pall ring and those obtained
with the tool using Ralu Flow, Ralu Ring, Hiflow ring, and NOR PAC ring, packing materials. ...... 96
Figure 47 Packing materials compared. Left to Right: Pall Ring, Hiflow ring, NOR PAC, Ralu Flow, Ralu
ring, Hackette. Source (Raschig Gmbh, 2018) except for Hiflow Ring which was obtained from
(RVT Process Equipment GmbH, s.f.) ............................................................................................. 96
Figure 48 Valtra Diesel - Biogas tractor. (Valtra, 2018) ................................................................................. 104

List of Tables
Table 1 Typical raw biogas characterization (Wellinger, et al., 2013) ............................................................. 20
Table 2 Comparison based on operating parameters and quality performance between upgrading
techniques. Sources (blue small font in the table): 1 (Kadam & Panwar, 2017), 2 (Hoyer, et
al., 2016), 3 (Bauer, et al., 2013), 4 (Ong, et al., 2014), 5 (Allegue & Hinge, 2011), 6 (Biosling
AB, 2012). ....................................................................................................................................... 36
Table 3 Comparison based on contaminant tolerance between upgrading techniques. Sources (blue
small font in the table): 1 (Kadam & Panwar, 2017), 2 (Hoyer, et al., 2016), 3 (Bauer, et al.,
2013), 4 (Ong, et al., 2014), 5 (Allegue & Hinge, 2011), 6 (Biosling AB, 2012). ............................. 37
Table 4 Constants reported by (Sander, 2015) used in Equations 17 and 18. ................................................ 44
Table 5 CO2 Henry's constants for Equations 17 and 18. Source author of the present study. ...................... 45
Table 6 Values of efficiencies, overpressure, additional temperature and others used in the power
calculations. Source ....................................................................................................................... 75
Table 7 Structure of the comparison runs. The values of flow and "from" "to" are approximations of the
values used. RB: Raw biogas flow, Lo Liquid flow, pf: pressure of the flash tank, ps: pressure
of the scrubber, Ts: temperature of the scrubber, Hs: height of the scrubber. ............................. 82
Table 8 Slip comparison results ....................................................................................................................... 87
Table 9 Compositions concentrations results ................................................................................................. 88
Table 10 Height calculation deviations results ................................................................................................ 90
Table 11 Sensitivity analysis results summary. The method the tool uses is CM —blue text—. .................... 92

1 Proposal
1.1 Background
Replacement of fossil fuels as an energy source is imperative to mitigate the climate change impact. Biogas
obtained from Anaerobic Digestion (AD) of organic matter is a promising option. The use of AD dates back to
ancient times. Countries like China and India have thousands of artisanal digesters. However, the raw biogas
has low heat value due to the presence of a high carbon dioxide (CO2) concentration. Therefore, upgrading
is often necessary depending on the final use of the biogas. For example, if it is injected into the natural gas
grid or used as Compressed Biogas Gas for vehicles (CBG), the methane content must be around 97%.
The industrial use of upgraded biogas did not experience a significant development until 2006 - 2007 mainly
in Germany, Sweden, and the United Kingdom as it can be seen in Figure 1 and Figure 2 (IEA Bioenergy, 2017).
Figure 1 Number of industrial AD plants commissioned each year in the world from 1981 to 2016. In total, there is
one plant that lacks an upgrading system and another one that performs only partial upgrading. (IEA Bioenergy, 2017)
Following (Wellinger, et al., 2013) or (Sibiya, et al., 2017), the sources for biogas production can be classified
as:
• Agricultural Sources that can be further classified as wastes and energy crops.
o Animal manure and slurries
o Plant residues
o Energy crops
• Industrial waste and byproducts
• Municipal organic waste
o Sorted solid organic waste
o Sewage
• Aquatic Biomass
According to (Wellinger, et al., 2013) the most important feedstock for the AD is the agricultural sources.
Nevertheless, according to (Sibiya, et al., 2017), the use of these biomass sources has reported process

instabilities and low efficiencies. The author also points out that co-digestion has been recommended as a
remedy to these issues.
There are two pathways to produce biogas, biochemical and thermochemical. The biochemical pathway
consists of producing biogas using microorganisms to process the biomass. The most widely used nowadays
is the AD. The thermochemical path consists of producing biogas using physical mechanisms to process the
biomass. Generally, two main techniques are used, pyrolysis and gasifier. While pyrolysis produces a mixture
of solid, liquid and gases, gasification processes will mainly produce only gases. The final products of these
thermochemical processes depend on the feedstock, process design, and ultimate purposes of the products
(Luque & Lin, 2016).
As a fuel, biogas has the potential to serve as a dispatchable energy source. This capability helps to balance
energy systems where intermittency of the source is high, like in Solar and Wind power. It can play an
essential role as ancillary services for power networks. For transport fuel, it holds a high potential with proven
technology – Compressed Natural Gas (CNG) – that has been successfully implemented in the past two
decades (Budzianowski & Brodacka, 2017).
Since one of the most used technologies to produce Biogas is AD, the use in situ offers the possibility for
agricultural dependent population to gain access to clean sustainable energy as a source for electricity,
heating, transport fuel, and cooking. The impact may boost welfare as well as considerably reduce the
environmental impact by reducing deforestation, replacement of fossil fuels, and reduction of greenhouse
gases (GHG) (IRENA, 2016).
Depending on the final use of the biogas, it is convenient to clean and upgrade it. Biogas can be used directly
– with minor cleaning – as an energy source for a Combined Heat and Power (CHP) unit. Nevertheless, the
demands of electricity and heat are seldom constant and equal to the biogas production. Having additional
uses or storage of upgraded biogas will improve the energy efficiency and flexibility of the system.
The typical characterization of biogas composition is presented in Table 1. Cleaning is the process of removing
the impurities and pollutants present in the raw biogas. Some of the most common ones are hydrogen
sulfide (H2S) and Ammonia (NH3). Upgrading is the process of increasing the CH4 concentration by reducing
the CO2 present in the mixture (Luque & Lin, 2016).
Hydrogen sulfide possesses a serious corrosive potential to equipment, and it can also produce SOX gases
when combusted. In order to eliminate these effects, the raw biogas must be cleaned. There are several
common ways of treating this issue, but one of the most effective is trough water scrubbing.
Figure 2 Total Number of upgrading plants per country until 2016 (IEA Bioenergy, 2017)

The presence of CO2 lowers the energy content of the biogas mixture, and it consumes energy to transport,
compress, heat or cool. Depending on the final use, it is more efficient to increase the CH4 concentration, so
the lost energy associated with its handling is reduced. Further, if the biogas is intended to be used as a
transportation fuel or injected to a natural gas network, it should comply with regulations that determine
the concentration levels of CH4 as well as other components, like nitrogen, oxygen, and water.
Table 1 Typical raw biogas characterization (Wellinger, et al., 2013)

Compound Unit Range
Methane (CH4) mol-% 35 – 75
Carbon dioxide (CO2) mol-% 15 – 50
Nitrogen (N2) mol-% 0–5
Oxygen (O2) mol-% 0–1
Hydrogen sulfide (H2S) ppm 10 – 15.800
Ammonia (NH3) ppm 0 – 150
Total chlorine (Cl) mg/m3 0 – 100
Total fluorine (F) mg/m3 0 – 100
Siloxanes mg/m3 0 – 0.2
Ethylbenzene ppm < 0.34
Copper µg/m3 < 20
Even though the AD is spread along the globe, the upgrading is still not implemented massively. Only
industrial operations have incorporated the process in recently. As depicted in Figure 1 and Figure 2 the
number of upgrading units have grown only since 2006, mainly in Germany, Sweden, and United Kingdom
(IEA Bioenergy, 2017).
The upgraded-biogas added capacity and total cumulative is shown in Figure 3. The average size of an
installed plant from 2007 to 2016 is 930 Nm3/h. Until 2016, the total worldwide installed capacity is only
527 000 Nm3/h (IEA Bioenergy, 2017). This capacity production is only a small fraction of the natural gas
consumption per hour for the same year of approximately 404 million Nm3/h (BP, 2017).
The plant size is depicted in Figure 4. The average size is 1 022 Nm3/h. The most common technology type is
the water scrubber, followed by membrane, chemical scrubber, Pressure Swing Adsorption (PSA), organic
physical scrubber, low-pressure swing adsorption (LPSA), amine scrubber, and cryogenic separation. The
capacity mix for 2016 is presented in Figure 5. The water scrubbing techniques double its closest competitor.
Figure 3 Added capacity year by year from 1981 to 2016. The red curve depicts the total cumulative capacity in Nm3/h.

There is no consensus about the classification of the biogas plant regarding its size. For this study, a plant
producing 100 Nm3/h or less is considered “small-scale.” This classification follows the one suggested by
(VALORGAS, 2011). Nevertheless, other authors as (Wellinger, et al., 2013) consider small-scale systems only
up to 100 kW (approximately 25 Nm3/h of raw biogas).
Figure 4 Plant type and size in Nm3/h distribution until 2016 (IEA Bioenergy, 2017).
Regarding the small-scale plants with upgrading, only 42 out of 548 are smaller than 100 Nm3/h. For these
small systems, the most used technology is membrane, followed by PSA, water scrubber, other not identified,
and organic scrubber. Concerning the number of units of the 19, eight are membrane, five are PSA, four are
water scrubbers, one is an organic scrubber, and one is not identified.
Figure 5 Left: Total capacity technology distribution mix in 2016. Right: Sizes 0 – 100 Nm3/h range technology capacity
mix (IEA Bioenergy, 2017).
According to (Lems & Dirkse, s.f.), for small-scale plants to be economically feasible, the best approach is to
use the biogas locally or as compressed biogas as vehicle fuel (CBG). They found a limit between 20 and
25 Nm3/h to achieve a payback time of the upgrading plant of five years. Nevertheless, if the system has a
CHP unit, the payback can be reduced to three to four years. It is important to notice that their study relies
on membrane separation technique.

An innovative example of small-scale upgrading system is the one produced by Biosling. It consists of a water
scrubber process that develops in a rotating coil filled with biogas and water. According to (Biosling AB, 2012)
the biogas can be upgraded to 95% CH4 content using only the rotating coil. The biogas rated flow for the
smallest unit is 0 to 36 Nm3/h. See further down for a more detailed explanation of the system.
There is an increasing focus on small-scale biogas operations, for example, the “Record Biomap” which is a
research project that intends to “bridge the gap between research and industry and to accelerate innovation
in small and medium scale biomethane production, thus shorten the time to market of the most promising
technologies.” Some of the processes that are supported by the project are: Algal-bacterial upgrading
(University of Valladolid), Blue BONSAI membrane technology (Apex), Ash filter (RISE), in-situ methane
enrichment (RISE), vacuum pressure swing adsorption (NeoZeo), vacuum swing adsorption Biogame
(AzzeroCO2 SRL), MR methane reactor (ED Biogas International AB), Pressureless cryogenic conversion of
biogas into dry ice and liquid biomethane (Hochschule Landshut), G-PUR Membrane technology (CEBB
CentraleSupélec), Biological methanation (Electrochea GmbH), and Biogas to bio-LNG system (Cryo Pur).
(Rogstrand, 2018).
Water, as the main consumable of water-upgrading systems, has an important characteristic that makes it a
potential feasible technology to be implemented in small scale. In general, water is available where biomass
as feedstock is located for AD applications, like farms, or agricultural locations. The supply of chemicals, or
special consumables like membranes or spare parts for moving objects, increases considerably the cost of
operation for remote locations, which is often the case of agricultural sites. Technical assistance costs also
build up the farther the plant is located from central cities. The use of water as the absorber of CO2 reduces
these expenses.
Another benefit of using water as the absorber is the low environmental impact. Handling dangerous
materials carries the risk of leaks, accidents, and pollutions due to malfunctioning of the equipment. On the
other hand, the final disposal of used materials increases the operational costs, especially if the system is an
isolated location.
Using water as an absorber can be done in two ways. The simplest way is to pass it through the scrubbing
column just once and dispose it of. The other way is to regenerate the water after the scrubbing process in a
stripper column. It is evident that the first method demands a large fresh water supply, like a river or lake.
The impact of this method is that the CO2, H2S, and other substances will go into the wastewater, and if no
treatment is performed then these compounds will pollute the water. The latter method releases the CO2
and H2S from the water in the stripper column. Nevertheless, after some cycles the water must be replaced
because of contaminants build up.
As it can be seen, water scrubbing imposes an environmental impact, but it is case dependent, and it should
be evaluated as a system. There are some alternatives to treat the wastewater of an upgrading plant, but the
methods are dependent on the biogas composition, especially the pollutants present.
In general, all upgrading techniques use approximately the same amount of energy (Budzianowski, et al.,
2017). It is important to notice that an upgrading plant needs to be flexible due to the fluctuations in the
available raw biogas flow. This is because, whatever needs to be upgraded is dependent on the balance
between the CHP unit, the AD production rate, the upgraded fuel demand, the cost of electricity and
substitute fuel (e.g. petrol or diesel), among other variables that influence the final amount of biogas that
goes through one path or another. Figure 6 illustrates this concept.

Figure 6 Biogas paths. The amount of biogas used in each path is dependent on several factors. The flow into
upgrading is, thus, variable.
Commonly, isolated communities have unsatisfied energy needs. Biogas can be the solution, but the current
development of upgrading systems have been centered around big scale systems with high quality and strict
regulations for the final biogas composition (Bauer, et al., 2013). Those studies, pilot plants and current
operation plants are not intended for such isolated locations. Therefore, another piece of the energy shift
towards renewables and increased sustainability of energy systems is to find a solution for these needs.
Biogas holds a promising potential where simple technologies, low environmental impacts, ease of use, and
low cost can be combined to supply affordable and clean energy for all.
1.2 Problem Formulation

International Micro Biogas AB (IMBAB) is a startup company that is investigating small-scale biogas systems.
Their focus is to provide self-standing units capable of providing an essential share of the energy demand of
small farms and agricultural locations. The units would consist of an anaerobic digester, an upgrading unit,
and a CHP plant. IMBAB has preselected high-pressure water scrubbing technique as the upgrading
technology.
One of IMBAB’s goals is to develop “in-house” knowledge about their processes. Thus, to be able to predict
and model their biogas systems. Modeling the upgrading unit will provide valuable information about the
internal energy consumption; the upgraded quality of the biogas; the water flow needs; the sizes of accessory
equipment like compressors, blowers, water pumps, and coolers, and the columns physical dimensions, I.E.,
height and diameter.
Their request is to develop an Excel-based model that can provide all this information in a user-friendly way.
The user should be able to produce results in an agile manner without the need of investing hours to set up
the system.

1.3 Objective
The focus of this thesis is to develop a modeling tool that describes the performance of a small-scale water-
based scrubber system for biogas upgrading. Small-scale refers to a production rate of raw biogas between
10 and 100 Nm3/h. The results of the model must provide:
• The upgraded flow and quality
• The height and diameter of the upgrading column
• The methane loss of the system (see slip definition in page 27, section 2)
• The power demand for ancillary equipment, I.E., compressors, water pumps, air blower and coolers
• The energy balance of the system
1.4 Methodology
The methodology proposed is based on numerical, empirical and analytical models, with a comparison of the
model results against the results of similar models developed in a commercial software.
The project is based on the following hypotheses:
• The performance of an upgrading biogas system can be modeled by knowing the characteristics and
properties of the packing elements of the scrubbing column.
• The influence of the methane loss is profoundly influenced by the presence and operating
parameters of a flash tank.
The development of the model requires solving two different problems. One is solving the mass balance and
calculation of operation parameters of the system conformed by a scrubber, flash tank, and a stripper. The
second one is to calculate the height and diameter of the scrubber.
For the first problem —Solve the mass balance—, the challenge lays in the recirculation flows. The proposed
methodology to solve the system is to implement an iterative process where the recirculation flows are
updated in each step using the results of the previous step. This process is carried out until there is no
significant change in the flows. This convergence is reached if the difference between two consecutive steps
is less than a stopping value, typically set to 10-10.
The advantage of this iterative process is that it resembles the operation of the startup of the system, each
step resembles a transient period, and the behavior of the convergence process can be followed and
analyzed. If no solution is found, for example, if the flows tend to zero or infinity, or there is a residual value
that does not decrease with additional iterations, there is the possibility to see the evolution of the process,
and infer the possible problems and propose solutions to overcome the difficulties.
One of the disadvantages of the process is that it might require large amounts of processing time if the
number of iterations rises. Nevertheless, since the equations used in the mass balance are all solved
analytically, each iteration process is expected to be significantly short in time. Another disadvantage is that
a non-convergence case takes a long time to be pointed out since the iterations rise and the residue does not
change, or the flows would tend to zero or infinity. This inconvenience could be avoided if some checks are
performed before starting the iteration process. For example, one could check that the flow of water is
enough to carry out the maximum separation, meaning that the slip would be very close to zero. If this check
is passed, it means that there is a solution to the separation process.
For the second problem —calculate the height and diameter of the scrubber— the proposed methodology is
to implement a variation of the one proposed by Billet and Schultes in two core publications (Billet, 1995)

and (Billet & Schultes, 1999). The variation consists in splitting the column into slices and applying the Billet
and Schultes methodology to solve for the height and diameter of the slice.
The Billet and Schultes methodology is an application of the HTU-NTU method using Higbie’s penetration
model as the governing mechanism for the mass transfer. In this method, a critical parameter to calculate is
the liquid holdup of the column. This value is calculated by iteration, and it varies from zero to one since it is
a fraction of the void volume. In this case, there is an asymptotic behavior of the function. The proposed
methodology for this iteration is solving by sweeping the function from 0 to 1 by 0.1 increments of the liquid
holdup. When the function changes sign, it means a solution between the two points has been found. Then
a new sweeping process would be carried out between those points where the solution was found but with
0.01 increments. The increments will reduce until a stopping value has been reached, typically between 10-
10
and 10-16. For example, let us assume that the first sweeping process shows that the solution is found
between 0.2 and 0.3. Then a second sweeping process is carried starting with 0.2, followed by 0.21, 0.22 and
so on. Let us assume that the solution is found between 0.25 and 0.26; then a third sweeping process is
carried out using 0.251, 0.252, 0.253… The process finishes when a sufficiently small interval of a solution is
achieved.
This iteration method has a potential problem of jumping over the asymptote. If such is the case, a solution
is to start with a smaller increment sweeping process, for example using 0.01. The processing time is
increased but is more likely to achieved convergence.
Another important aspect of the Billet and Schultes methodology is that it is a combination of a theoretical
framework developed using fluid and hydrodynamics, and empirical correlations result from extensive
experimentations. The correlations are introduced to correct or adjust the theoretical model to the presence
of the packing material. The correlations used are the ones reported by the authors in the referred
publications.
1.5 Implementation
The project is divided into three general stages. First, a literature study and a theoretical framework will be
developed. The second stage comprises the model development and implementation in Visual Basic for
Applications (VBA). A comparison will be made against the same model carried in the commercial, specialized
software like ASPEN Plus. The third and last stage consists of performing a sensitivity analysis on some
dominant parameters and evaluate their impact on the performance of the tool.
1.6 Problems and Limitations

The main limitation identified is the scarcity of available data on small-scale biogas upgrading systems. In
literature, it is usually considered small-scale those systems with throughput less than 100 Nm3/h. The aim
of this study is centered at sizes between 10 and 100 m3/h.
Biogas is a mixture of several gases, but the main components are methane (CH4) and carbon dioxide (CO2).
The primary contaminant substance is hydrogen sulfide (H2S). Other contaminants are commonly present
like ammonia (NH3) or volatile organic compounds (VOC). For this study, only CH4 and CO2 will be considered
as the core upgrading need. All other substances present will be disregarded.
The results and sources are theory-based, and no laboratory tests, experimental data or real application will
be developed or studied.

The physical details of the equipment are not covered nor analyzed in the study. The influence or limitations
due to material compatibility, physical strength or resistance, controlling processes and other limitations are
neglected in this study.
The process to be studied is based on physical absorption. All chemical reactions dynamics and related details
are not part of the scope of the project and are thus disregarded.
Due to the low speed of biogas generation processes, all phenomena to be evaluated and analyzed will be
considered only a steady-state process. The transient phenomena between the different stages of the
digesting process are neglected and disregarded.
All models are maximum second-order mathematical models. The influence of higher order terms is
neglected in the current study.
The water to be used in the process will be considered as drinking quality water and the effects of different
substances present in the water, like minerals or dissolved gases, will be neglected.
1.7 Expected Outcomes

A VBA model implemented in Excel as hosting application of a water-based, small-scale biogas system, where
different parameter can be changed like raw gas flow, raw gas composition (CH4, CO2), process pressure and
temperature of the different streams, and pressure losses where relevant.
A written report detailing the mathematical framework, the model structure, results, sensitivity analysis,
discussion, conclusions and possible future studies.

2 Upgrading Techniques
This section will discuss the most used techniques for upgrading. A comparison of benefits and drawbacks
will be presented for each. The following descriptions are mainly based in (Cheremisinoff, 2000)
An important concept used in biogas upgrading is the “slip.” It is defined as the amount of methane that is
removed —and lost— from the original biogas flow. Slip can be expressed as the total amount lost in Nm3/h,
mol/h or kg/h, or as a fraction of the total incoming methane flow.
2.1 Physicochemical Upgrading Systems

2.1.1 Absorption
Absorption is the flow of molecules of a substance into another substance. Absorption can be either physical
or chemical. Physical absorption depends on the solubility of a substance into the other. Chemical absorption
includes chemical reactions between the substances.
The principle is based on the absorption difference between the gases. For biogas, using water as the
absorber, CO2 is around 25 times more soluble than CH4 at 25°C. For other absorbers, commonly referred as
amine, like polyethylene glycol, monoethanolamine (MEA), diethanolamine (DEA) the difference is even
more significant, one to two magnitude orders. This higher solubility reduces the absorber flow, operating
pressure, column diameter and equipment installation costs. Another benefit is the lower CH4 slip, typically
0.04 to 0.1% - one order of magnitude lower than water scrubbing-. Nevertheless, the energy requirements
to regenerate, the contamination of the absorber due to the presence of H2S or NH3 are drawbacks of these
absorbers. Due to complexity to regenerate, contaminant buildup monitoring, amine breakdown, and
foaming this upgrading technique is not used in small-scale systems (Deublein & Steinhauser, 2011) (Ong, et
al., 2014).
Since the substances must get into direct and close contact with each other, it is necessary to achieve the
highest transfer surface between them. Usually, and this is the case in the present study, one of the
substances is a gas and the other is a liquid. To make them get in contact, there is some typically used
equipment found in the industry like plate columns and packed towers among others.
The absorber can be regenerated and then reused in a continuous process. The regeneration process is often
called stripping —the contrary to absorption—. The stripping process is the same physical process that
happens in absorption but with opposite direction. Diffusion of molecules in the liquid-gas interphase have
two driving forces. One is the concentration difference in the liquid-liquid side, and the other one is the
partial pressure difference in the gas-gas side. See section 3 further where the process is detailed.
In the following subsections, the equipment that is commonly used for mass separation absorption is
described. There are other types of equipment like Venturi scrubbers and cooler absorbers that are not
covered in this study since their application is related to specific chemical processes.
2.1.1.1 Agitated Vessels
The gas and the liquid are introduced in a closed vessel, and mechanical agitation will provide the intimate
contact between the substances. This method is useful when a slow reaction occurs within the substances.
One drawback is that when a continuous flow is needed, a series of vessels will have to be used. Another
disadvantage is that it presents more pronounced pressure drops than other continuous flow equipment.

2.1.1.2 Bubble-plate Towers

Plate towers and packed columns are, typically, counterflow equipment that operates continuously. They are
also used for distillation purposes. The liquid falls in steps through trays, while the gas flows up and passes
through cups that form bubbles in the liquid contained in the tray. Figure 7 presents the basic principle. This
method is useful when a low liquid rate is needed, when a slow reaction is needed, when there is a difficult
absorption task, or if there is a risk of clogging due to solids deposition. The latter, since it is easier to clean
via utility holes than packed towers-. Pressure losses are slightly higher than in packed towers (will be
described below.)
Figure 7 Left: Bubble plate tower. Right: Picture of a tray with bubble caps for a distillation column. Figure adapted
and picture obtained from (Sölken, 2018).
2.1.1.3 Spray Towers

Spray towers are empty vessels where at the top a sprayer is found. The sprayer will atomize the liquid to
form small droplets which are free to fall. In their trajectory, they meet a gas flow going upward. The
effectiveness of the method depends on the application. There are some disadvantages in its application.
The total surface tends to reduce as the droplets fall due to the coalescence effect, which takes place when
two or more droplets merge to form a bigger one. Another drawback is that the liquid in contact with the gas
is only a small layer of the surface of the droplet, the center of the droplet will remain at initial concentration,
thus reducing the effectiveness of the process. For difficult absorption, a series of towers can be
implemented. (Cheremisinoff, 2000)
2.1.1.4 Wet scrubbers – Packed Towers
Wet scrubbers -packed towers- consist of a column filled with what is called packing material. The liquid flows
down contacting the packing material. The sum of all the wetted surfaces accounts for a large total absorbing
surface. The gas can flow co-current, cross-current or countercurrent, being the later the most common. The
liquid flow is controlled so that the column does not flood, and all the packing material gets wet. If the flow
is too low, some part of the packing will remain dry reducing the total absorption area. If the flow is too high,
the column will fill up with liquid and become flooded.
In some cases, the liquid load is several times higher than the vapor flow, and the liquid becomes the
continuous phase where the gas bubbles upward. This operation state is called phase inversion, and one of
the characteristics is that it presents a relatively high-pressure drop of the gas. (Billet, 1995)

The general process is graphically explained in Figure 8. The liquid is recirculated between the scrubber and
the stripper. Depending on the biogas contamination the liquid is replaced more or less frequently due to
chemical or thermal breakdown or degradation, and contamination buildup. This process can use different
washing liquids like water or amines. A common practice is to use a flash recovery tank, where part of the
CH4 dissolved in the liquid is recovered by a drastic pressure drop.
There are several versions of the process, depending on the source and final use of the biogas, some of the
options are (Wellinger, et al., 2013), (Bauer, et al., 2013), and (Allegue & Hinge, 2011):
• One or two stages of compression with cooling and hydrate separation upstream from the scrubber.
• H2S removal treatment upstream from scrubbing —external from digester or in situ—.
• With or without a flash unit.
• With or without regeneration of water.
• With or without waste gases treatment.
• With or without water filtration.
Figure 8 Water scrubber process. Adapted from (Wellinger, et al., 2013) and (Bauer, et al., 2013).
Depending on the scrubbing substance and the final use of the biogas a dryer is needed downstream or
upstream of the scrubbing column. For example, if water or amine are used, the dryer is installed
downstream since the gas will exit saturated. The most used scrubbing substances, water and amine solution,
will separate CO2 and H2S at the same time, but H2S will be regenerated in the stripping process and must be
treated in the waste gas flow. Therefore, a common practice is to clean the biogas from H2S upstream of the
scrubber.
There is a wide range of commercial packing materials available. In Figure 9, some examples of packing
material are shown.

Figure 9 Different industrial packing materials. 1 Cylindrical ring. 2 Berl-Saddle. 3 Novalox® Saddle. 4 Pall® ring
(metallic). 5 Pall® ring (plastic). 6 Interpack®. 7 VSP®. 8 Igel®. 9 Novalox® - M. 10 VFF.Power-Pack®. Images obtained
from (Vereinigte Füllkörper-Fabriken GmbH & Co. KG, 2016)
Another option for packing material is the so-called structured or stacked packing. These consist of organized
and specially arranged packing units. In general, they have lower pressure drops and higher liquid flows but
can result in higher building costs and difficulty to perform cleaning maintenance routines. Two examples of
structured packing are shown in Figure 10.
Figure 10 Structured packing. Images obtained from (Raschig Gmbh, 2018).
2.1.2 Adsorption
Adsorption is the physical process of adhesion of molecules of a substance on the solid surface of other
substance. Contrary to absorption, the adsorbed substance does not penetrate the other substance; it stays
adhered to the surface. Adsorption can be physical called physisorption, or chemical called chemisorption.
(Cheremisinoff, 2000)
The physical principle behind physisorption is driven by intermolecular interaction, electrostatic, van der
Waals forces, or by the physical structure of the pores in the adsorber. It is the interaction between these
different properties of the adsorber and the adsorbate that will determine the degree of adsorption.
For physical adsorbers, regenerations is also a common practice. The process is driven by one or a mix of
pressure, temperature of concentration swing.
Chemisorption is based on the phenomenon that chemical bonds will develop on the surface with none or
little, diffusion between the adsorbate and the adsorber. Typically, these reactions are exothermic and with
greater heat generation than the heat rejection taken place when physisorption occurs.

The most used adsorber is active carbon. It is considered as a physical adsorbent. Commercially, it is found
in natural grain —granular—, pellets or powder. The granular type is mostly used for gas-solid adsorption
processes. The size of the pore and the properties of the adsorbate define how effective the adsorption
process is.
The gas-adsorption process is designed in different ways, but the most common is the bed type. A flow of
gas is forced to go through a granular active carbon bed. The adsorption process will decrease as the
concentration of the adsorbate increases in the adsorber.
The adsorption phenomenon is widely used in industry and especially in the chemical sector. Regeneration
can be done in multiple ways depending on the adsorbate and if chemisorption or physisorption is in place.
For this study, only the pressure swing adsorption process will be described as is widely used in the biogas
upgrading process.
2.1.2.1 Pressure Swing Adsorption (PSA)
In the biogas upgrading process, this technique is usually carried out using active carbon as the adsorber
material, and regeneration occurs with a pressure drop to free the adsorber of the CO2. The process is
graphically described in Figure 11.
Figure 11 PSA plant configuration. Four columns continuous process. Image adapted from (Wellinger, et al., 2013).
As it can be seen, is a batch process, where adsorption takes place in one vessel, while regeneration takes
over in the other vessel. When the adsorber is close to saturation, the vessels are switched. Regeneration is
achieved by lowering the pressure —pressure swing— in the saturated vessel. The typical setup for
continuous operation is a four-column configuration, known as the Skarstrom cycle (Hoyer, et al., 2016). In
this setup, one of the vessels is always depressurizing, so there is a continuous flow of upgraded biogas.
Typical adsorbent materials are active carbon, zeolites, silica gels, and carbon molecular sieves. According to
(Hoyer, et al., 2016) there is active research in metal-organic new adsorbents and combining different
adsorbers into a single column to clean and upgrade at the same time.
One of the typical drawbacks of this system is that the raw biogas must be cleaned from H2S and dried before
entering the columns. H2S will react with the adsorber while CO2 will be physically adsorbed. The chemical
binding will limit the lifespan of the adsorber as an increasing loss of active material will be available through
the cycles. To avoid this problem, an active carbon filter is placed upstream the columns and H2S, as well as
other contaminants, are removed and thus protect the adsorber in the column (Hoyer, et al., 2016).

2.1.3 Membrane Permeation

Another technique to separate gases, liquids, or mixes of them is done using the selective permeability
properties of one or a set of membranes. For biogas upgrading, hollow polymeric fibers are used. One crucial
factor is the selectivity of the membrane to allow the flow of CO2 and avoid CH4 slip (Hoyer, et al., 2016).
Typically, the membranes used are sensitive to liquids, oils, and impurities. Some conditioning should be
carried out before the upgrading. Low concentrations of H2S will be separated with CO2, in addition, they do
not harm the membrane markedly. Nevertheless, if condensates of water are present, they will react to form
acids that do harm the membrane and will significantly lower the lifespan of the system. Other contaminants,
like NH3 when dissolved in water from condensation, or volatile organic compounds (VOC) can harm the
membrane irreversibly. Commonly a set of filters or a scrubber is used before passing the gases through the
membrane (Hoyer, et al., 2016).
Commonly, operating pressures are around 10 – 20 bar. Compared to other upgrading processes, the
pressure is high. This elevated pressure can be useful for subsequent compression for storage or compressed
biogas as vehicle fuel (CBG). Nevertheless, for some other applications, the pressure must be reduced
meaning that the energy stored as pressure will be lost or has to be recovered using additional equiptment
(Ong, et al., 2014).
Depending on the application, the process can consist of one, two or three stages of membranes as shown
in Figure 12. Adding stages will further reduce the recycled gas and the CH4 slip, but it will increment the
energy intensity of the process (Hoyer, et al., 2016).
Figure 12 Different membrane upgrading configurations. Image adapted from (Hoyer, et al., 2016).
Organic membrane materials are preferred over inorganic due to higher surface-volume ratio, superior
structural integrity, lower production cost, advanced stage of development, stable at high pressures (Ong, et
al., 2014). The hollow fibers are bundled into small units to allow ease of maintenance and replacement. This
set up of several units working in parallel give this upgrading system the ability to perform well at partial
loads, by closing some of the membrane units (Wellinger, et al., 2013).

Figure 13 Gas - Liquid membrane technique.
Other than gas-gas upgrading membrane technique, there is also liquid-gas technique shown in Figure 13.
One of the key differences is that it operates near to atmospheric pressure. Liquid and gas are in
countercurrent fashion; the liquid is slightly under-pressure relative to the gas, so it is prevented to flow into
the gas stream (Andriani, et al., 2014).
2.1.4 Cryogenic Distillation

Cryogenic distillation is based on the fact that CO2 has a higher condensation temperature than CH4.
Therefore, it is possible to separate the liquid or solid easily. Operating pressures range from 18 to 30 bar
with condensation temperatures between -45 and -59°C. One benefit is that H2S, which has a condensation
temperature of -60°C at 1 bar, also is removed from the gases. Depending on the source of the biogas other
contaminants can also be present and the removal upstream is desirable to avoid solid clogging (Ong, et al.,
2014).
One of the benefits of the cryogenic system is that it also separates Oxygen (O2) and Nitrogen (N2)—present
as contaminants— since their boiling points are even lower than the CH4 point. This option implies that CH4
will be removed from the stream as a liquid and can be used as liquefied biogas (LBG). Each of the products
can be extracted with a high purity level. Even CO2 has the potential to be graded as food standard, making
most of the by-products potentially marketable (Ong, et al., 2014).
Cryogenic distillation seems to be a promising technology, even if it has not been used commercially in large-
scale plants yet (Hoyer, et al., 2016). According to (IEA Bioenergy, 2017) there is only one plant in the
Netherlands with an installed capacity of 200 Nm3/h.
2.1.5 Biosling
Biosling is a unique biogas water scrubbing system. It consists of a plastic tube, configured as a rotating coil
that is fed alternatively with biogas and water. As the coil rotates, it compresses the biogas, and at the same
time, CO2 is dissolved. At the end of the coil, the carbonated water is separated from the upgraded biogas.
This application is a co-current configuration, and the efficiency is lower than for counter-current schemes.
Since the CH4 final concentration is up to 94%, an additional water column is used to increase the
concentration to a level of 97% (Allegue & Hinge, 2011).
A study made by (Andersson & Sag, 2016), where they perform a comparison between Biosling and a
conventional water scrubber, concludes that Biosling has a higher energy demand per Nm3 upgraded than
conventional water scrubbers. Nevertheless, an interesting remark states that if upgrading was done only up
to 94% or less, the final water scrubber column is not needed, and the technology would be a better option
than its compared competitor.

Some of the benefits of Biosling are the lower water consumption and small size. The technology regenerates
the water used in a conventional striper as depicted in Figure 14. The unit packing size is a container which
is easy to transport and install.
Figure 14 Biosling process scheme. Figure obtained from (Biosling AB, 2012)
2.2 Biological Upgrading Systems

According to (Toledo-Cervantes, et al., 2017) Biological based technologies have been successfully proven at
pilot and full-scale sizes. Some biological techniques are described here.
2.2.1 Photosynthetic Upgrading

A mix of CO2 algae fixation and sulfur-oxidizing bacteria are used to upgrade raw biogas. This technology
cleans the H2S and does the upgrading at the same time. Some of the benefits are:
• low running cost,
• the processed biogas has the potential to be injected into natural gas grids,
• the biomass algae product of upgrading can be used as fertilizer, and
• the algae also have phytohormones which act as natural insecticides.
Some drawbacks are the extensive land use and high investment costs mainly due to the drying process of
the algae when used as fertilizer (Toledo-Cervantes, et al., 2017).
2.2.2 Hydrogenotrophic CO2 Reduction to CH4

Hydrogenotrophic methanogens are bacteria that consume CO2 and hydrogen and produce CH4 according to
Equations 1 and 2 below. The AD can be described as a three-stage process as shown in Figure 15. The
reductive CH4 formation is done by methanogens and accounts for 30% of the CH4 produced in the process.
Once the hydrogen is produced is consumed together with CO2 immediately to form CH4 and water as
products.
By adding hydrogen from an external source, upgrading can be obtained within the AD process. It aims at
consuming the CO2 that is produced in the other stages of the process. To achieve the reduction, the

hydrogen must be dissolved in the slurry and reach the methanogens. This technique has, however, two
major drawbacks. The first one is low mass transfer from gaseous hydrogen into dissolved hydrogen in the
slurry. This low solubility can be compensated for by additional agitation of the slurry and the head gases.
The additional agitation consumes energy and might have additional impacts on the process like foam
formation. The second drawback is the pH increase due to the lower CO2 concentration; higher pH levels
inhibit the CH4 production (Sofer & Zaborsky, 1981).
This upgrading in situ process has been evaluated by (Luo, et al., 2012). The results show a reduction from
38% CO2 in the control digester versus 15% in the experimental setup and a 22% CH4 production increase in
the experimental digester.
Figure 15 AD process description (Sofer & Zaborsky, 1981).
2.2.3 Biotrickling Filtration Upgrading (Deublein & Steinhauser, 2011)

The biotrickling system is very similar to a scrubbing column. The difference lies in that a layer of
microorganisms is inoculated in the packing material and hydrogen is added to produce CH4 following the
reaction in Equation 1. Studies like the one developed by (Dupnock & Deshusses, 2017) show that the
implementation of a bioreactor with inoculated Hydrogenotrophic Methanogens bacteria will effectively
upgrade raw biogas with CO2 efficiency removal up to 96%. Nevertheless, the positive technical feasibility,
there are two main drawbacks, axial-differential bacterial growth, meaning that bacteria will grow at
different rates at different heights of the column, and high pH levels which inhibits bacterial activity.
4𝐻2 + 𝐶𝑂2 → 𝐶𝐻4 + 2𝐻2 𝑂 (1)
If the growth of the bacteria is significant, the CO2, hydrogen, and CH4 balance with the biomass produced
according to Equation 2, where 𝐶5 𝐻7 𝑂2 𝑁 is the composition of the bacterial biomass.
0.131𝐶𝑂2 + 0.004𝑁𝐻4 + 0.5𝐻2 → 0.115𝐶𝐻4 + 0.004𝐶5 𝐻7 𝑂2 𝑁 + 0.266𝐻2 𝑂 (2)

2.3 Upgrading Technology Comparison

Since each technology has benefits and drawbacks depending on scale, the source of biomass, the final use
of upgraded biogas and the geographical location (VALORGAS, 2011), a technical comparison is presented in
Table 2. The sources are referenced in the caption of the table. A similar table is presented by (Allegue &
Hinge, 2011) and all data is coherent within both tables. An interesting observation is that the electricity
demand is very similar for all of them. The amine upgrading technique has a remarkably lower electricity
demand, but a heat demand instead. According to (Allegue & Hinge, 2011), cryogenic upgrading can present
a substantial electricity demand, but the final product is LBG which accounts for the additional energy input.
Biological conversion/upgrading is not included in the table since most of the reports refer to study
experiments or pilot plants. The main aim of some of the biological techniques —like CO2 reduction to CH4 in
the digester— is to reduce the CO2 from the stream, but not to upgrade to the full extent. Therefore, it is not
a fair comparison to physicochemical processes.
Chemical absorption has an outstanding low CH4 slip. The reason is that the chemical reaction is highly
selective and CH4 physical absorption is extremely low in the solution. This benefit has boosted this
technology because of its inherent potential to comply with CH4 slip regulations —typically around 0.5%—.
Other technologies rely on waste gases post-treatment to ensure the required reduction of slipped CH4 (Ong,
et al., 2014).
Table 2 Comparison based on operating parameters and quality performance between upgrading techniques. Sources
(blue small font in the table): 1 (Kadam & Panwar, 2017), 2 (Hoyer, et al., 2016), 3 (Bauer, et al., 2013), 4 (Ong, et al.,
2014), 5 (Allegue & Hinge, 2011), 6 (Biosling AB, 2012).
CH4 Energy
Pressure Heat Temp CH4 Slip Consumables
Upgraded Demand
bar kWh/Nm3 °C % % kWh/Nm3
1 1 4 1 1 1 3
Water Scrubber 4 -7 No 20 - 40 < 1% > 97% < 0.25 Water 0.04 - 0.4 liter/Nm3
Mechanism: 5- 8 2 < 2% 1 93 - 98% 4 0.23 - 0.3 3 Water, Antifouling agent 4
Physical Absorption 7 - 20 4 1% 2
1% 3
1 - 3% 4
1 1 1 1 1 1 3
Amine Scrubber ≈0 Yes 50 - 100 < 0.1% > 99% < 0.15 Water 0.03 liter/Nm3
Mechanism: 2 3 3 2 4 3 3 3
≈0 0.55 120-150 0.10% 99% 0.12 - 0.14 Amine 0.00003 kg/Nm
Chemical Absorption 0 - 10 4 0.5 - 0.75 5 35 - 50 4 0.10% 3 Amine, Antifouling agent 4
100 - 180 5 0.04 - 0.1% 4
Glycol Scrubber 4 -7 1 Yes 1 10 - 100 1 2 - 4% 1 > 96% 1 0.24 - 0.33 1 No water 3
Mechanism: 5- 8 2 < 0.2 5 55 - 80 5 0.5-2% 2 95 - 98% 4 Activated charcoal 3
Physical Absorption 4- 8 4 10 - 20 4 1.5 - 4% 4 Physical solvent 4
PSA 4 -7 1 No 1 5 - 30 4 < 3% 1 > 96% 1 0.25 1 No water 3
Mechanism: 1 - 10 4 3 - 6% 1 95 - 98% 4 0.2 - 0.3 3 Activated charcoal 3
Physical Adsorption 1 - 1.5% 2 Adsorbent 4
1.8 - 2% 3
1 - 3.5% 4
Membrane 10 - 20 2 No 5 25 - 60 4 0.50% 2 85 - 99% 4 0.2 - 0.3 3 No water 3
Mechanism: 7 - 41 4 0.50% 3 Activated charcoal 3
Permeation 0.5 - 20% 4 Membranes 4
Cryogenic 18 - 30 4 No 5 - 59 - -45 4 0.5 - 3% 4 96 - 98% 4 0.20 - 028 5 Glycol, refrigerant 4
Mech: Condensation 17 - 26 5 0.45, 0.72 5
Biosling 10 3 No 3 1% 3 97% 3 0.15 - 0.25 3 Water 3
Mech: Physical Absorption 0.2 - 0.4 6
One of the challenges in the upgrading process is handling contaminants. Table 3 presents a summary of the
influence of different contaminants in respect to each upgrading technique. One interesting observation is
the potential of cryogenic upgrading. It can handle all contaminants including O2 and N2 which are extremely

difficult to separate. Another benefit is that the end products can be marketable as high-grade
substances (Ong, et al., 2014).
Water scrubbing adds O2 and N2 in a tiny fraction as contaminants into the upgraded biogas. Nevertheless,
their influence is minor and disregarded for most applications, even for grid injection or for CBG (Bauer, et
al., 2013).
Table 3 Comparison based on contaminant tolerance between upgrading techniques. Sources (blue small font in the
table): 1 (Kadam & Panwar, 2017), 2 (Hoyer, et al., 2016), 3 (Bauer, et al., 2013), 4 (Ong, et al., 2014), 5 (Allegue &
Hinge, 2011), 6 (Biosling AB, 2012).
H2S O2, N2 VOC NH3 Water
Pre-Clean Pre-Clean Pre-Clean Pre-Clean Pre or post
No 1 Go into biogas 2 Main part goes to 2 Removed in process 2 Post 1
Water Scrubber
stripper and condensate water
Mechanism: No, goes into the 2 Contamination added 4 Removed from biogas, 4 Removed from biogas, 4 Post 2
Physical Absorption stripper preferred pre-cleaned preferred pre-cleaned

No 3 Post 4
Pre-removal 4
preferred
Not needed / 4
preferred
Yes 1 Go into biogas 2 Main part goes to waste 2 Main part goes to waste 2 Post 2
Amine Scrubber
gases and condensate gases
Part to waste gases, 2 3 Partial removal from 4 Removed from biogas, 4 Post 4
O2 reacts irreversibly
Mechanism: part with biogas biogas, preferred pre- preferred pre-cleaned
with amine. N 2 goes to
Chemical Absorption cleaned
waste gases
Yes 3 4
O2 removal required,
N2 goes to biogas
Yes 4
Main part goes to 2 Go into biogas 2 Removed from biogas, 4 Removed from biogas, 4 Post 2
Glycol Scrubber
striper air preferred pre-cleaned preferred pre-cleaned
Not needed / 4 Partial removal 4 Main part goes to striper 2 Tolerates minor 2 Pre - 4
Mechanism:
preferred air concentrations, Main preferred
Physical Absorption
part goes to striper air
PSA Yes 1 Into waste gases 2 Not tolerated. 2 Not tolerated. 2
No, if low 2 3 Removed from biogas, 4 Removed from biogas, 4

Can remove O2 and N2,
Mechanism: concentration preferred pre-cleaned preferred pre-cleaned
but with additional
Physical Adsorption
cost.
Yes 3
Yes 4
Yes 3 Partial removal 4 Not tolerated. 2 Usually removed with 2 Pre 2

Membrane
condensates while
Preferred 4 3 Goes to biogas 4 Removed from biogas, 4 None 4
Mechanism: N2 to biogas, O2 to
Permeation waste gases preferred pre-cleaned
Low concentrations, 2 part go the biogas, part 2
part go the biogas, to waste gases

part to waste gases
Preferred 4 Go into biogas 2 Removed from biogas, 4 Removed from biogas, 4 Pre 2
Cryogenic
preferred pre-cleaned preferred pre-cleaned
Mechanism: Low concentrations 2 Complete removal 4 Tolerates high 2 Tolerates high 2 Pre - 4
Condensation tolerated, removed concentrations, concentrations, preferred

in first stages removed in first stages removed in first stages

2.4 Advantages and Disadvantages of Upgrading Techniques

As discussed previously, the implementation of an upgrading technique depends on biomass source, final
use of biogas, operating conditions and geographical location. The comparison is made as a guide to highlight
the differences, potential uses and most important challenges of each technique independent of the
equipment. It also proves helpful to check the selection of the technology done by IMBAB. The following
analysis is adapted from (Allegue & Hinge, 2011).
• High-Pressure Water Scrubbing:
Advantages Disadvantages
− Relatively simple technique. − Consumes water, not recommended for
− Does not use chemicals. locations with water scarcity.
− Low environmental impact of leakages − Bacterial growth inside the scrubber.
and waste management. − H2S must be kept under 500 ppm.
− Tolerance and separation of H2S up to − Introduced O2 and N2 as contaminants.
500 ppm. − Requires relatively low temperatures of
− Does not require heat addition. water and gas (10°C).
− High flexibility of operation, capacity can − If H2S and NH3 are not removed waste
be changed by gas and water flows, gases and water must be treated.
pressure and temperatures. − CH4 slip can be high: up to 6% without flash
− The water flow can remove NH3. recovery, up to 1% with recovery.
− Many plants and providers available. − Drying post-treatment necessary.
− CO2 is not recoverable.
• PSA
− No water or liquid needed. − H2S can degrade the adsorber. It might be
− No chemicals used. necessary the use of a pre-cleaning step.
− Depending on adsorber part of the pre- − Raw gas drying step needed upstream.
cleaning process can be avoided. − High CH4 slip.
− Good option for “small” scale operation. − Sophisticated and highly controlled
− Relative low energy demand. process.
− Regenerative process. Many cycles − Intrinsic batch process, to make it as
without adsorbent replacement. continuous process a four-vessel
− No need for drying after upgrading. configuration is needed.
− Removes O2 with additional cost.

• Glycol Scrubber (Physical)

− High CO2 solubility, lower pumping needs − Heat needed to regenerate the glycol.
compared to water. − Relative high investment costs.
− High selectivity to CO2 resulting in a lower − If glycol is diluted in water, the plant
CH4 slip. performance is diminished.
− Possibility to remove H2S and NH3. If high − Glycol replacement or adjustment due to
concentrations are present, a pre- losses or degradation.
treatment must be implemented. − Possible environmental impact if leakages
− No water requirement. or malfunctioning.
− Lower corrosion in equipment. − Drying downstream of the upgraded
biogas is needed.
• Amine Scrubber (Chemical)

− Extreme CO2 selectivity resulting in extra − Relative high investment costs.
low CH4 slip. − Need for heat as energy input.
− Near to atmospheric pressure. − Potentially corrosive.
− No water consumption. − High environmental impact if leakages.
− Low electricity demand. − Foaming.
− Possibility to recover the CO2 as a high- − Salts precipitation. Reduction of system
grade marketable product. performance.
− Since one of the energy needs is heat at a − Need to replace or add amine solution.
relatively low temperature, the source − Chemical manipulation associated risks.
can be waste heat. − O2 irreversibly reacts with the amine
− No bacterial growth due to high pH levels. solution. Amine degradation.
− H2S pre-cleaning required.
• Membrane
− No water consumption. − High CH4 slip if just one stage is used.
− Low CH4 slip for two or more stages. More stages higher investment cost and
− Relative low energy demand. higher operational costs.
− Suitable for “small” scale operation. − Recent technology reliability is uncertain.
− Flexibility at partial loads. − If high moisture content, H2S and drying
− No drying necessary –neither upstream are necessary upstream.
nor downstream-. − NH3 and VOC can degrade the membranes
− Partial removal of N2 and O2. permanently.
− If low H2S concentration there is no need − High cost of membranes, becomes an
for pre-cleaning as long the process important issue if accelerated membrane
operates over the dew temperature. degradation is present.
− Ease of maintenance due to the possibility
of isolation of individual units.
− Small footprint, flat units.
− Small transportation packages.

• Cryogenic
− No chemicals nor water needed. − High energy demands.
− Potential to deliver extra high CH4 − New implementation of technology, just
concentrations. one plant in operation, with no historical
− Low CH4 slip. data available.
− CO2 as a marketable product. − High technical requirements due to low
− Possibility to produce LBG directly in the temperatures and relatively high
upgrading process –with little extra pressures.
energy added-.
− Possibility to remove N2 and O2 from
biogas stream —implies the liquefaction
of CH4—.
Giving the circumstances of rural locations and isolated communities, it can be argued that the high-pressure
water-scrubbing technique has the potential to be implemented with no significant obstacles. On the other
hand, it would benefit the users to access clean energy to satisfy needs of heat, electricity, and fuel for
transportation. IMBAB’s technology selection seems to be coherent with their focal market.
According to (Enefalk & Ersöz, 2016), for biogas to be used as fuel for transportation in private fleets, it must
be upgraded to a range between 78% and 83%. To successfully achieve this goal an upgrading system must
be implemented. To promote the development of the biogas sector, it is necessary to provide specialized
tools that aid the implementation process. This need is the reason why a modeling tool aimed at describing
the operating variables of an upgrading system is needed.

3 Water Scrubbing Columns

The fundamentals of water-scrubbing were discussed in Subsection 2.1.1.4 “Wet scrubbers – Packed
Towers.” The present section extends the description further. It defines the mechanism for the height and
diameter calculation following the methodology proposed originally by (Billet, 1995) and extended later by
(Billet & Schultes, 1999)
The section is divided into four subsections. The first one defines the mass balance and basic equations that
describe the general operation of the column. Two important concepts are introduced, the operating curve
and the equilibrium curve. The second subsection establishes the fluid dynamics equations that are proposed
to model the flow behavior in packed columns. The third subsection introduces the methodology “Height of
the transfer unit – Number of transfer units” (HTU - NTU). The fourth subsection describes the models used
for the calculations of the fluid properties: density, dynamic viscosity, solubility, diffusivity, and surface
tension.
The sources of most of the equations, figures and theoretical foundation are (Billet, 1995) and (Billet &
Schultes, 1999), except for Subsection 3.1.2 “Equilibrium curve” and Subsection 3.4 “Fluid Properties
Calculation” where the different sources are given accordingly throughout the text.
3.1 Mass transfer in columns

Two core concepts describe the operation of a scrubbing -absorption- column. The first concept is the
operating line which refers to the rate of absorption at which the column operates, and the other concept is
the equilibrium curve, which refers to the maximum load of a species a liquid can dissolve given the
composition of the same species in the vapor phase and the pressure and temperature of the media.
3.1.1 Operating line

The mass transfer phenomenon that takes place in a biogas high-pressure water scrubber is based on the
different absorption properties of water for CO2 and CH4. A schematic representation is shown in Figure 16.
The water enters the top of the column with a low concentration of gases dissolved and exists with a high
concentration at the bottom. On the other hand, the raw biogas enters the column at the bottom with a high
concentration of CO2 and exits the column at the top upgraded.
Figure 16 Scrubbing process. Left: Packed column. Center: Equilibrium and operating curves given in molar load units.
Right: Equilibrium and operating curves given in molar fraction units. Figures adapted from (Billet, 1995).

Before starting with the analysis, it is convenient to make some comments on the notation used.
• Sub-index “u” denotes the bottom of the column.
• Sub-index “o” denotes the top of the column.
• Sub-index “2” means that the variable is related to CO2.
• Sub-index “4” means that the variable is related to CH4.
• All flows are expressed in [kmol/h] except if stated differently.
• Variables starting with “y” (lowercase) relate to mole fraction in the vapor phase. The units of “y”
are [kmol/kmol] meaning kmol of species “a” per kmol of vapor.
• Variables starting with “Y” (uppercase) denote load in the vapor phase. The units of “Y” are
[kmol/kmol] meaning kmol of species “a” per kmol of species “b.” The relation between “y” and “Y”
is stated in Equation 3.
• Variables starting with “X” (uppercase) denote the load in the aqueous or liquid phase. The units of
“X” are [kmol/kmol] meaning kmol of species “a” per kmol of H2O”.
𝑦
𝑌= (3)
1−𝑦
Using Figure 16 as a reference, the mass balance for the column can be expressed as:
𝐿 ∙ (𝑋𝑢𝑎 − 𝑋𝑜𝑎 ) = 𝑉𝑢 ∙ 𝑦𝑢𝑎 − 𝑉𝑜 ∙ 𝑦𝑜𝑎 (4)
Where 𝐿 is the molar flow of water, 𝑋𝑢𝑎 is the load of species “a” in the aqueous phase exiting the column,
𝑋𝑜𝑎 is the load of species “a” in the aqueous phase entering the column, 𝑉𝑢 is the molar flow of the vapor
entering the column, 𝑉𝑜 is the molar flow of the vapor exiting the column, 𝑦𝑢𝑎 the mole fraction of species
“a” entering the column, and 𝑦𝑜𝑎 is the mole fraction of species “a” exiting the column.
For biogas, the primary two components are CO2 and CH4. Neglecting the other components, the vapor flows
entering the column can be expressed as:
𝑉𝑢 = 𝑉𝑢2 + 𝑉𝑢4 = 𝑉𝑢 ∙ 𝑦𝑢2 + 𝑉𝑢 ∙ 𝑦𝑢4 (5)
𝑉𝑜 = 𝑉𝑜2 + 𝑉𝑜4 = 𝑉𝑜 ∙ 𝑦𝑜2 + 𝑉𝑜 ∙ 𝑦𝑜4 (6)
For the moment, consider that the flow of CH4 is constant, meaning that CH4 does not get dissolved in H2O.
𝑉 = 𝑉𝑢4 = 𝑉𝑜4 (7)
Using the concept of load

𝑉𝑢2
𝑌𝑢2 = (8)
𝑉
𝑉𝑜2
𝑌𝑜2 = (9)
𝑉
Equation 4 for CO2 can be written as

𝐿 ∙ (𝑋𝑢2 − 𝑋𝑜2 ) = 𝑉 ∙ (𝑌𝑢2 − 𝑌𝑜2 ) (10)

Rearranging Equation 10 gives a key relationship between the flows in the column
𝐿 (𝑌𝑢2 − 𝑌𝑜2 )
= (11)
𝑉 (𝑋𝑢2 − 𝑋𝑜2 )
Equation 10 can also be written as, which is known as the “operating line” of the column
𝐿
𝑌𝑜2 = 𝑌𝑢2 − ∙ (𝑋𝑢2 − 𝑋𝑜2 ) (12)
𝑉
1 (13)
𝑋𝑜2 = 𝑋𝑢2 − ∙ (𝑌𝑢2 − 𝑌𝑜2 )
𝐿
(𝑉 )
The slope of the operating curve is the relation 𝐿⁄𝑉 and it corresponds to a straight-line equation. See the
center graph of Figure 16 where the operating line is plotted.
In reality and for the present study, CH4 does slip and 𝑉 is not constant. The slip can vary from values less
than 0.4% to 18% depending on the pressure and temperature of the scrubber and flash tank if present.
The definition of slip is expressed either as flow as in Equation 14 or as a fraction as in Equation 15.
𝑠𝑙𝑖𝑝 = 𝑅𝐵4 − 𝑉𝑜4 (14)
𝑅𝐵4 − 𝑉𝑜4 𝑠𝑙𝑖𝑝

𝑠𝑓 = = (15)
𝑅𝐵4 𝑅𝐵4
Where 𝑅𝐵4 is the molar flow of CH4 in the raw biogas. To be clear in the notation 𝑠𝑓 is the slip as a fraction
and 𝑠𝑙𝑖𝑝 is the slip as the molar flow of CH4.
See Subsection 4.2 “CH4 Absorption Model” where the description of the calculation of the molar flow of CH4
is presented.
3.1.2 Equilibrium curve

The maximum amount of a species that a liquid can dissolve under equilibrium conditions limits the operation
of the scrubbing column. The operating line must always be over the equilibrium curve as shown in Figure 16.
The equilibrium curve is given by
𝑦 = 𝑚𝑦𝑥 ∙ 𝑥 (16)
Where 𝑚𝑦𝑥 is a function of pressure, temperature and the properties of the species. Note that 𝑦 and 𝑥 are
lowercase denoting molar fractions.
Following (Sander, 2015) publication, Henry’s law allows calculating 𝑚𝑦𝑥 . The law states that the amount of
a species dissolved in a solution is proportional to the partial pressure of that species in the vapor phase. The
proportionality is given by Henry’s constant
𝑐𝑎 = 𝐾𝑇 ∙ 𝑝𝑎 (17)

Where 𝑐𝑎 is the concentration of species “a” in the aqueous phase, 𝐾𝑇 is Henry’s constant and 𝑝𝑎 is the
partial pressure of species “a” in the vapor phase. Henry’s constant is temperature dependent and it can be
described according to
∆𝐻 1 1
(− 𝑆𝑂𝐿 )∙( − ) (18)
𝐾𝑇 = 𝐾𝐵 ∙ 𝑒 𝑅 𝑇 𝑇𝐵
Where ∆𝐻𝑆𝑂𝐿 is the change in the enthalpy of the solution, 𝐾𝐵 is Henry’s constant at a base temperature,
∆𝐻𝑆𝑂𝐿
and 𝑇𝐵 is the base temperature. Values for − and 𝐾𝐵 can be found in the compilation reported by
𝑅
(Sander, 2015). Table 4 presents the values for CH4 and CO2 found in the mentioned compilation.
Table 4 Constants reported by (Sander, 2015) used in Equations 17 and 18.

𝑲𝑩
𝒎𝒐𝒍 ∆𝑯𝑺𝑶𝑳
Species −
[ 𝟑 ] 𝑹
𝒎 ∙ 𝑷𝒂
CH4 1.4 × 10−5 -1400
CO2 3.4 × 10−4 -2400
In the present study, for CO2 the values used are reported in Table 5 instead of those reported in Table 4. The
four values used were obtained by fitting the laboratory data reported by (Houghton, et al., 1957). The
validation of the constants was made overlying the figure found in (Carroll, et al., 1991) with the values
plotted using Equation 17 with the fitted values reported in Table 5. Figure 17 shows the result of the
validation. Note that the temperature range of interest is between 0 and 50°C. The model starts deviating at
temperatures around 80°C far from the operation of a scrubbing column.
Figure 17 Validation of constants fitted to laboratory data. In light blue the results of this study in black original data.
The original plot was extracted from (Carroll, et al., 1991).

Table 5 CO2 Henry's constants for Equations 17 and 18. Source author of the present study.
∆𝑯𝑺𝑶𝑳
Range − for CO2
𝑹
0 to 45°C, 0 to 10 bar -2411.23
0 to 45°C, 10 to 20 bar -1824.48
45 to 100°C, 0 to 10 bar -1953.91
45 to 100°C, 10 to 20 bar -2009.19
𝑚𝑜𝑙
The units for 𝑐𝑎 are [ 𝑚3 ] which mean “moles of diluted species per cubic meter of solution.” To convert the
𝑚𝑜𝑙
units to obtain the molar fraction of a species in water or the molar mixing ratio the aqueous solution [ ]
𝑚𝑜𝑙
which mean “moles of diluted specie per mol of solution” the following expression is used
𝑀𝐻2 𝑂 𝑚𝑜𝑙𝑎
𝑥𝑎 = 𝑐𝑎 ∙ [ ] (19)
1000 ∙ 𝜌𝐻2 𝑂 𝑚𝑜𝑙𝐻2 𝑂
Where 𝑀𝐻2 𝑂 is the molecular weight of H2O and 𝜌𝐻2 𝑂 the density of H2O. Note that the density of H2O varies
with temperature. The values of density used in this study are linearly interpolated from the values reported
𝑔
by (Harvey, 1998). The molecular weight of H2O used is 18.015 [𝑚𝑜𝑙].
Equation 20 is obtained by inserting Equation 19 in 17 and assuming that the partial pressure of the
components of the biogas behaves according to Dalton’s law.
1000 ∙ 𝜌𝐻2 𝑂
𝑦𝑎 = 𝑥𝑎 ∙ (20)
𝑀𝐻2 𝑂 ∙ 𝐾𝑇 ∙ 𝑝
Where 𝑝 is the operating pressure of the column.

The term to the right of Equation 20 is the 𝑚𝑦𝑥 function in Equation 16. As expected, it is dependent on
temperature and the species involved through Henry’s constant, and to pressure trough the operating
pressure of the column.
For a given operating point -defined by the operating line- there is a maximum equilibrium concentration
according to Equation 16. For example, for a point Y in Figure 16, corresponds the X molar load in the
operating line and 𝑌𝑒 and 𝑋𝑒 in the equilibrium curve. Notice that the molar fraction values in Equation 16
must be converted to molar load values to plot both curves in the same graph.
Since the raw biogas is the given flow, it is assumed that its composition is known and a target composition
for the upgraded biogas is given. The variables to solve for are then, the flow of water, and the molar load in
the aqueous phase at the exit of the column.
𝑦𝑒
𝑦𝑒 = 𝑚𝑦𝑥 ∙ 𝑥 ∴ 𝑌𝑒 = (21)
1 − 𝑦𝑒
1 𝑥𝑒
𝑥𝑒 = ∙𝑦 ∴ 𝑋𝑒 = (22)
𝑚𝑦𝑥 1 − 𝑥𝑒
If plotted in a molar load system the operating line is a straight line and the equilibrium curve a non-linear
function, concluding that the absorption process is not linear.

3.2 Column Operation - Fluid Dynamic Description

The high-pressure biogas scrubber column studied is a packed countercurrent absorber where the water
trickles down the column while the gas flows upwards. The fluids perform mass transfer by the interaction
taken place in the interfacial area between both phases.
The fluids behavior depends on the geometry and properties of the packing elements, as well as the loads,
the properties of the fluids, and the operating conditions. The methodology followed in this study assumes
that the fluid dynamics can be modeled as mix flow through tubular channels. The deviations from the model
are corrected by the introduction of several packing constants, the definition of specific flow resistance
factors, and by a-dimensional analysis and estimation of exponents for fluid numbers like Reynolds, Froude,
and Weber.
To describe the fluid dynamics of the column the following concepts and notation are defined:
• Molar, volume, or mass flow: Defined as the flow for each phase. The notation used is:
o 𝐿𝑥 , 𝐿𝑚𝑎𝑠𝑥 , 𝐿𝑣𝑜𝑙𝑥 for aqueous flows. Note that if there is no sub-index, it means that it is a
molar flow. Sub-index “x” will define where in the column the flow is defined for, and
what species it is relating to (2 for CO2 and 4 for CH4.) If there is no number and no
sub-index meaning the position on the column, it relates to the water flow (since it
is constant throughout the column). If there is no number and a sub-index for the
position, it means it is the sum of all the flows of all the species in the related phase
including water.
For example, 𝐿𝑚𝑎𝑠𝑢 means the liquid flow of H2O, CO2 and CH4 at the bottom of the
column (exiting).
o 𝑉𝑥 , 𝑉𝑚𝑎𝑠𝑥 , 𝑉𝑣𝑜𝑙𝑥 for the vapor flows. Note that if there is no sub-index, it means that it is a
molar flow. Sub-index “x” will define where in the column the flow is defined for, and
what species it is relating to (2 for CO2, 4 for CH4.) If there is no number and a sub-
index for the position, it means it is the sum of all the flows of all the species in the
related phase, in the related position.
In the case of volumetric flow if an uppercase N appears in the sub-indices, then it
relates to the normalized flow conditions (0°C and 1 Atm). Otherwise, it relates to
flow conditions (pressure and temperature)
For example, 𝑉𝑣𝑜𝑙𝑁𝑜2 means the Normalized volumetric flow of CO2 at the top of the
column (exiting).
• Load: Flow of a phase —liquid or vapor— through the cross-section of the column. It is denoted by a
lowercase “u” and sub-indices “L” for liquid and “V” for vapor. It is calculated as:
𝐿𝑣𝑜𝑙
𝑢𝐿 = (23)
𝐴
𝑉𝑣𝑜𝑙
𝑢𝑉 = (24)
𝐴
where A is the cross-section area of the column.

• 𝑢
̅̅̅𝐿 : Local liquid velocity: Is the velocity of the liquid in a specific reference point. See the right side
of Figure 18. It is calculated as
ℎ𝑙
𝑢
̅̅̅𝐿 = (25)
𝑢𝐿
• ̅̅̅𝑉̅: Average effective vapor velocity. See the right side of Figure 18.
𝑢
• 𝜀 : Void volume: The empty space inside the column. The void is defined by the fraction of empty
volume to total volume. It is important to clarify that the void volume is measured at no load, it only
corresponds to the geometry of the packing. Each type of packing has the void fraction as a given
constant by the supplier. It is denoted as 𝜀. Units [[𝑚3 ⁄𝑚3 ]
• 𝑎: Packing area: The area per volume of a given packing material denoted by a and with
units [𝑚2 ⁄𝑚3 ].
• 𝑎ℎ : Hydraulic area: The area per volume of a given packing material denoted by a and with
units [𝑚2 ⁄𝑚3 ].
• ℎ𝑙: Liquid holdup: It is the amount of liquid that the column holds dynamically. This holdup is
proportional to the loads and properties of the fluids and the packing.
• Δ𝑝: Pressure drop: It is the average pressure drop per meter of the vapor load in the column.
Four key variables must be found to model the column. Three are interdependent variables the loads 𝑢𝐿 , 𝑢𝑉 ,
and the liquid holdup ℎ𝑙. The fourth variable is the pressure drop Δ𝑝. The calculation of the three
interdependent variables is described in Subsections 3.2.1 and 3.2.2, the pressure drop is not covered in the
present study, but it can be found the referenced work of (Billet, 1995) and (Billet & Schultes, 1999).
3.2.1 Loading and Flooding Points

The liquid phase flows downward while the vapor phase flows upward as schematically represented in
Figure 18. The liquid is pushed down by the gravity force, and it is pushed up by the frictional force exerted
by the vapor phase in the interfacial area. At a specific liquid load and vapor velocity these forces equalize,
the liquid velocity at the interface becomes cero, and the liquid begins to hold up. That point is called the
loading point.
Figure 18 Left: Liquid holdup and phase distribution for a low liquid load. Center: High liquid load. Right: Schematic
representation of packing and phase interaction. The right figure was adapted from (Billet, 1995)
After the loading point has been reached, if the vapor velocity keeps rising or the liquid load increases the
holdup will rapidly increase. There is a point where for an additional increase in the loads the holdup tends

to infinity. This point is known as the flooding point. The loading and flooding points are graphically shown
in Figure 19.
The left side in Figure 18 represents a low flow and low holdup. The liquid develops a film covering the
packing. This film provides the surface where mass transfer between phases takes place. Once the holdup
increases, the empty spaces are reduced as it is shown in the center figure. Notice that the empty spaces are
where the vapor phase flows.
One of the goals of the packing is to assure the mixing of the liquid, so the concentration of the dissolved
species is homogeneous between the bulk and the exposed surface. This mixing is achieved by continually
renewing the surface of the liquid which forms the interfacial area.
A representation of the points is shown in Figure 19. The higher the vapor velocity and the liquid load the
thicker the liquid film and consequently a higher holdup.
Figure 19 Loading and flooding points. Figure adapted from (Billet, 1995)
Following the analysis and methodology of (Billet, 1995), Equation 26 models the flow of the column in all
the flowing range. It relates the column load —liquid and vapor—, its holdup, properties of the packing, and
the properties of both phases. The derivation of this equation can be found in Billet’s mentioned work.
1 𝑔 𝜉 𝑎
𝑎2 ∙ 𝜂𝐿 ∙ 𝑢𝐿 = ℎ𝑙 𝑛 ∙ ( ∙ 𝜌𝐿 − ∙ ∙ 𝑢2 ∙ 𝜌 ) (26)
3 4 ℎ𝑙 ∙ (𝜀 − ℎ𝑙)2 𝑉 𝑉
Where 𝑔 is the gravitational acceleration, 𝜉 the resistance to flow, 𝜂𝐿 the dynamic viscosity of the liquid
phase, 𝜌𝐿 the density of the liquid phase, and 𝜌𝑉 the density of the vapor phase.
The “n” in the exponent in Equation 26 is 1/3 for laminar flow in tubular channels. For turbulent flow in
randomly dumped packing is approximately 2/3.
Equation 27 is an empirical expression that calculates the liquid flow resistance 𝜉 as fa unction of the molar
flows, viscosities, densities, and a constant C that is exclusive for each packing. This constant accounts for

the shape and surface of the packing. There are two constants for each packing one for the loading point 𝐶𝑆
and another one for the flooding point 𝐶𝐹𝑙 .
𝑔
𝜉𝑥 = −2𝑛𝑆
1
𝐿 𝜌 2 𝜂 𝑚 (27)
𝐶𝑥2 ∙ [𝑉 ∙ ( 𝜌𝑉 ) ∙ ( 𝜂 𝐿 ) ]
𝐿 𝑉
if 𝑥 = 𝑆 (loading point), then 𝑚 = 0.4.

if 𝑥 = 𝐹𝑙 (flooding point), then 𝑚 = 0.2.
The exponent 𝑛𝑆 depends on which is the continuous phase. For low liquid flow, and low operating pressure,
the continuous phase is the vapor phase. In this case, the liquid trickles downward through the packing. If
the liquid load or operating pressure increases the volume of liquid increases related to the volume of gas. If
the increase continues it will get to the inversion point. At this point, the liquid becomes the continuous
phase while the vapor bubbles up through the packing. Mathematically, the inversion point is reached when
the flow parameter Ψ is equal to 0.4. This flow parameter is defined by
1
𝐿 𝜌𝑉 2 (28)
Ψ= ∙( )
𝑉 𝜌𝐿
The exponent 𝑛𝑆 is defined according to
𝑛𝑆 = −0.326 if Ψ ≤ 0.4
(29)
𝑛𝑆 = −0.723 if Ψ > 0.4
𝐶𝑆 and 𝐶𝐹𝑙 are also corrected depending on the value of the flow parameter according to
𝜂 𝐿 0.1588
𝐶𝑆 = −0.695 ∙ 𝐶𝑆 ∙ ( )
𝜂𝑉
if Ψ > 0.4 (30)
𝜂 0.1028
𝐶𝐹𝑙 = −0.6244 ∙ 𝐶𝐹𝑙 ∙ ( 𝐿 )
𝜂𝑉
𝐶𝑆 and 𝐶𝐹𝑙 in the right side of Equation 30 are the original values given by the manufacturer.
Note that 𝜉 is only defined for two points and Equation 27 can only be used in Equation 26 if one of the two
points is being calculated.
3.2.1.1 Loading Point
By definition, the loading point is reached when the local fluid velocity ̅̅̅
𝑢𝐿 becomes cero. This occurs for a
certain liquid load denoted by 𝑢𝐿𝑆 . According to (Billet, 1995) the vapor load for this particular point is
given by
1
𝑔 ℎ𝑙𝑆 𝜌𝐿 2 (31)
𝑢𝑉𝑆 = (𝜀 − ℎ𝑙𝑆 ) ∙ ( ∙ ∙ )
𝜉𝑆 𝑎 𝜌𝑉

To be able to evaluate Equation 31 it is necessary to know the holdup at the loading point. By inserting
Equation 31 in Equation 26 and solving for the holdup
1 2
12 𝜂𝐿 3 𝑎ℎ 3 (32)
ℎ𝑙𝑆 = ( ∙ 𝑎2 ∙ ∙ 𝑢𝐿 ) ∙ ( )
𝑔 𝜌𝐿 𝑎
Where 𝑎ℎ is the hydraulic area of the packing. The concept is based in that for certain low liquid load the
packing surface might not get all wet. The thickness of the liquid film 𝑆0 is the result of dividing the total
holdup by the hydraulic area
ℎ𝑙
𝑆0 = (33)
𝑎ℎ
According to (Billet, 1995) the exponent of 2/3 in Equation 32 is the result of the extensive tests and
Equation 32 accurately predicts the holdup for all types of packing.
𝑎ℎ
The term 𝑎
is calculated according to
𝑎ℎ
= 𝐶ℎ ∙ 𝑅𝑒𝐿0.15 ∙ 𝐹𝑟𝐿0.1 if Re < 5
𝑎
(34)
𝑎ℎ
= 0.85 ∙ 𝐶ℎ ∙ 𝑅𝑒𝐿0.25 ∙ 𝐹𝑟𝐿0.1 if Re ≥ 5
𝑎
By inserting Equation 32 in Equation 31, the following expression is obtained for the vapor load.
1 1 2 1 1 1
𝑔 2 𝜀 1 12 𝜂𝐿 3 𝑎ℎ 3 12 𝜂𝐿 6 𝑎ℎ 3 𝜌𝐿 2
𝑢𝑉𝑆 = ( ) ∙ [ 1 − 𝑎 2 ∙ ( ∙ ∙ 𝑢𝐿 ) ∙ ( ) ] ∙ ( ∙ ∙ 𝑢𝐿 ) ∙ ( ) ∙ ( ) (35)
𝜉𝑆 𝑔 𝜌𝐿 𝑎 𝑔 𝜌𝐿 𝑎 𝜌𝑉
𝑎6
3.2.1.2 Flooding Point

The flooding point can be expressed mathematically as
𝑑𝑢𝐿
= 0 → 𝑢𝑉𝐹𝑙 (36)
𝑑ℎ𝑙
𝑑𝑢𝑉
= 0 → 𝑢𝐿𝐹𝑙 (37)
𝑑ℎ𝑙
By introducing these two conditions into Equation 26, the following expressions are obtained for the vapor
and liquid loads:
1 3 1 1
2 ∙ 𝑔 2 (𝜀 − ℎ𝑙𝐹𝑙 )2 ℎ𝑙𝐹𝑙 2 𝜌𝐿 2
𝑢𝑉𝐹𝑙 =( ) ∙ 1 ∙( ) ∙( ) (38)
𝜉𝐹𝑙 𝑎 𝜌𝑉
𝜀 2
𝑔 1 𝜌𝐿 3
3 ∙ (𝜀 − ℎ𝑙𝐹𝑙 )
𝑢𝐿𝐹𝑙 = ∙ 2 ∙ ∙ ℎ𝑙𝐹𝑙 ∙ (1 − ) (39)
3 𝑎 𝜂𝐿 2∙𝜀

The relation between the flooding loads, for a given flow ratio 𝐿⁄𝑉 is presented in Equation 40
𝜌𝐿 𝐿
𝑢𝐿𝐹𝑙 = ∙ ∙𝑢 (40)
𝜌𝑉 𝑉 𝑉𝐹𝑙
Notice that this relation between loads can also be applied for any given point in the column, it states that
the cross-section area is the same for both flows.
The holdup for the flooding point, which is obtained by inserting Equations 38, 39 and 40 in Equation 26 is
given by
3 (3
6 𝐿 𝜌𝑉 2 𝜂𝐿
ℎ𝑙𝐹𝑙 ∙ ∙ ℎ𝑙𝐹𝑙 − 𝜀) = ∙ ∙ ∙ 𝑎 ∙ 𝜀 ∙ ∙ 𝑢𝑉𝐹𝑙 (41)
𝑔 𝑉 𝜌𝐿 𝜌𝐿
Note that Equation 41 is a fourth-order equation and thus have several solutions. Only one of them is relevant
to the physical behavior. The liquid holdup must be less than the effective void fraction 𝜀, the left-hand side
of the equation must be positive meaning that ℎ𝑙𝐹𝑙 ≥ 𝜀 ⁄3.
An empirical relation between liquid holdup in the loading point and the liquid holdup in the flooding point
is presented in Equation 42. This equation provides satisfactory results, and it is recommended instead of
Equation 41. (Billet & Schultes, 1999)
𝜂𝐿 𝜌𝑤 0.05
ℎ𝑙𝐹𝑙 = 2.2 ∙ ( ∙ ) (42)
𝜂𝑤 𝜌𝐿
Where 𝜂𝑤 and 𝜌𝑤 are the dynamic viscosity and density of pure water. For the biogas scrubber, note that as
the water absorbs CO2 and CH4 its density increases, since its volume is assumed to remain constant.
3.2.2 Description of the Operating Intervals

To describe the flow for a given operating condition different than the loading or flooding point it is necessary
to provide equations for the liquid holdup and loads. There are two operating intervals; the first one goes
from no-load to the loading point and the second interval from the loading point to the flooding point.
The vapor load is calculated solving for 𝑢𝑉 in Equation 26, as depicted in Equation 43. Note that the vapor
load 𝑢𝑉 is a function of the liquid load 𝑢𝐿 and the liquid holdup, consequently the solution for this equation
is done iteratively.
1
𝑔 𝑎2 ∙ 𝜂𝐿 ∙ 𝑢𝐿 4 ∙ (𝜀 − ℎ𝑙)2 2 (43)
𝑢𝑉 = [( ∙ 𝜌𝐿 − )∙ ∙ ]
3 ℎ𝑙 3 𝜉 𝑎 ∙ 𝜌𝑉
The liquid load is related to the vapor load through Equation 40. The same equation is given in Equation 44
with general sub-indices.
𝜌𝐿 𝐿
𝑢𝐿 = ∙ ∙𝑢 (44)
𝜌𝑉 𝑉 𝑉
Equations for the liquid holdup depend on the interval of operation.

Interval from No-Load to Loading Point
This interval, as shown in Figure 19 is characterized by a “flat” liquid holdup. This flat characteristic is because
for an increase in the load —either liquid, vapor or both— there is no significant change in the liquid holdup.
Equation 26 can be used to calculate the liquid holdup for a given set of loads. This equation can be re-
written as
𝑛
2 2
𝑎 ∙ 𝜂𝐿 ∙ 𝑢𝐿 𝑎ℎ 3
ℎ𝑙 = [ ] ∙( ) (45)
𝑔 𝜉 𝑎 2 𝑎
3 ∙ 𝜌𝐿 − 4 ∙ ℎ𝑙 ∙ (𝜀 − ℎ𝑙)2 ∙ 𝑢𝑉 ∙ 𝜌𝑉
Note that in the use of this equation requires the knowledge of the flow resistance parameter 𝜉. Additionally,
this equation can only be solved iteratively, since ℎ𝑙 is in both sides of the equation and there is no analytical
solution for it.
In practical terms, the difference between the results of applying Equation 45 and Equation 32 —liquid
holdup in the loading point— is not significant. Thus, Equation 32 can be used for the referred interval. Note
that Equation 32 is only dependent on the liquid load, this is coherent with the description given in Figure 19.
Interval from the Loading Point to the flooding point
Once the liquid commences to holdup, the rate of change of the holdup rapidly grows as it is shown in
Figure 19. Equation 46 is an empirical equation that models the liquid holdup behavior in the operational
interval between the loading and the flooding points.
𝑢𝑉 13
ℎ𝑙 = ℎ𝑙𝑆 ∙ [1 + 1.2 ∙ ( ) ] (46)
𝑢𝑉𝐹𝑙
Note that this equation is coherent with Equation 42.
3.2.3 Column’s Diameter Selection

The diameter selection is a designer’s choice since its value will influence the loading and flooding points, as
well as the total height. In general, smaller diameters will result in lower pressure drops and lower columns.
Nevertheless, the wider the column, for the same operation pressure, the thicker the column’s wall which
results in higher investments.
By calculating the loading and flooding diameters for a given operational condition might serve as a guide in
the design process.
1
4 ∙ 𝐿 ∙ 𝑀𝐿 2 (47)
𝑑𝑥 = ( )
𝜋 ∙ 𝜌𝐿 ∙ 𝑢𝐿𝑥
Where 𝑀𝐿 is the molecular weight of the liquid and 𝑢𝐿𝑥 is the liquid load at the loading point or the flooding
point.
If the designer wishes to use a diameter where the liquid load is a fraction of the flooding, for example,
𝑢𝐿 = 0.8 ∙ 𝑢𝐿𝐹𝑙 , Equation 47 can be used inserting the desired liquid load.

3.3 HTU-NTU Method

With the fluid dynamics and the mass transfer description, the next step is to calculate the height and
diameter of the packed column. In this study, the general method followed is the HTU-NTU (Height of the
Transfer Unit–Number of Transfer Units) applying the methodology proposed by (Billet, 1995).
3.3.1 HTU-NTU General Description

The following description is based on (Bäbler, 2017).
Consider a section of the column as depicted in Figure 20. For the explanation of the method, it is supposed
that the flow of CH4 is constant. The mass balance for CO2 can be written as in Equation 48 for the vapor side
and as in Equation 49 for the liquid side.
Figure 20 Section of the scrubbing column. The flow of CH4 𝑽 and H2O 𝑳 constant.
𝑉 𝑉
∙ 𝑦(𝑧) − ∙ 𝑦(𝑧 + ∆𝑧) = 𝑎𝑝ℎ ∙ 𝑁 ∙ ∆𝑧 (48)
𝐴 𝐴
𝐿 𝐿
∙ 𝑥(𝑧) − ∙ 𝑥(𝑧 + ∆𝑧) = 𝑎𝑝ℎ ∙ 𝑁 ∙ ∆𝑧 (49)
𝐴 𝐴
Where 𝑎𝑝ℎ is the interfacial area where the mass transfer phenomenon takes place. Expanding the term
𝑦(𝑧 + ∆𝑧) using Taylor series, and by making ∆𝑧 → 0
0
𝑉 𝑉 𝑉 𝑑𝑦 𝑉 1 𝑑2 𝑦 2
∙ 𝑦(𝑧) − ∙ 𝑦(𝑧) − ∙ ∙ ∆𝑧 − ∙ ∙ 2 ∙ (∆𝑧) = 𝑎𝑝ℎ ∙ 𝑁 ∙ ∆𝑧 (50)
𝐴 𝐴 𝐴 𝑑𝑧 𝐴 2 𝑑𝑧
𝑉 𝑑𝑦
− ∙ = 𝑎𝑝ℎ ∙ 𝑁 (51)
𝐴 𝑑𝑧
𝐿 𝑑𝑥
− ∙ = 𝑎𝑝ℎ ∙ 𝑁 (52)
𝐴 𝑑𝑧
Where 𝑁 is the molar flux correspondent to the mass transfer between phases. The flux units are
[𝑘𝑚𝑜𝑙⁄(𝑚2 ∙ 𝑠)], while the flows units are [𝑘𝑚𝑜𝑙⁄𝑠]. According to (Billet, 1995) and (Kolev, 2006), Higbie’s
penetration model describes the mass transfer process phenomenon in packed-columns. Due to the packing,

the flows constantly mix forcing the interphase to be renewed. Thus, it can be assumed that the mass transfer
occurs by non-steady state diffusion (Billet, 1995).
According to (Crittenden, et al., 2012), the penetration model assumes a constant interphase renewal. It
considers packets of liquid that interact with the vapor phase during a contact time “t.” For example, for
vapor to liquid mass transfer, the longer the contact time, the higher the concentration of the dissolved vapor
in the liquid on a packet as shown in Figure 21.
Figure 21 Penetration model - Higbie Model. The time t of residence of the liquid packet is the time needed to flow
through a bubble of diameter d. The concentration n the liquid is cL and in the vapor phase cV.
According to (Kolev, 2006), in Higbie’s model, the molar flux can be calculated according to
𝑁 = 𝛽𝑉 ∙ (𝑐𝑖 − 𝑐𝑏 ) = 𝛽𝑉 ∙ 𝜌𝑚𝑜𝑙 𝑉 ∙ (𝑦𝑖 − 𝑦𝑏 ) (53)
𝑁 = 𝛽𝐿 ∙ (𝑐𝑖 − 𝑐𝑏 ) = 𝛽𝐿 ∙ 𝜌𝑚𝑜𝑙 𝐿 ∙ (𝑥𝑖 − 𝑥𝑏 ) (54)
Where 𝛽 is the mass transfer coefficient of Higbie, 𝑐𝑖 and 𝑐𝑏 are the molarity concentrations at the interphase
and at the bulk respectively, and 𝜌𝑚𝑜𝑙 is the molar density of the liquid or vapor phase. It is assumed that at
the interphase equilibrium exists. Therefore, the sub-index 𝑖 is replaced for 𝑒 and the sub-index 𝑏 is left blank
since all the concentrations are referred to the bulk value. The mass transfer coefficient 𝛽 is given by
1
1 𝐷𝑥 2 (55)
𝛽𝑥 = 2 ∙ ( ∙ )
𝜋 𝜏𝑥
Where 𝐷𝑥 is the Diffusivity in the liquid or vapor phase, and 𝜏 is the time of residence. The higher the
diffusivity the greater the mass transfer becomes. On the other hand, a longer time of residence result in a
lower mass transfer. Since, in packed-columns, the interphase is replaced constantly the residence time is
expected to be short.
For the liquid side as an example, inserting Equation 54 in Equation 52
𝑉 𝑑𝑥
− ∙ = 𝑎𝑝ℎ ∙ 𝛽𝐿 ∙ 𝜌𝑚𝑜𝑙 𝐿 ∙ (𝑥𝑒 − 𝑥) (56)
𝐴 𝑑𝑧

Separating variables and rearranging
𝐿 1 𝑑𝑥
− ∙ ∙ = 𝑑𝑧 (57)
𝐴 ∙ 𝜌𝑚𝑜𝑙 𝐿 𝑎𝑝ℎ ∙ 𝛽𝐿 (𝑥𝑒 − 𝑥)
Note that the first term on the left side of Equation 57 is the liquid load 𝑢𝐿 . Integrating from the bottom of
the column to the total height
𝑥𝑜 𝐻
𝑢𝐿 𝑑𝑥
− ∙∫ = ∫ 𝑑𝑧 (58)
𝑎𝑝ℎ ∙ 𝛽𝐿 𝑥𝑢 (𝑥𝑒 − 𝑥) 0
The height is of the column is calculated
𝑥𝑢
𝑢𝐿 𝑑𝑥
∙∫ = 𝐻𝐿 (59)
𝑎𝑝ℎ ∙ 𝛽𝐿 𝑥𝑜 (𝑥𝑒 − 𝑥)
Similar for the vapor side
𝑦𝑢
𝑢𝑉 𝑑𝑦
∙∫ = 𝐻𝑉 (60)
𝑎𝑝ℎ ∙ 𝛽𝑉 𝑦𝑜 (𝑦𝑒 − 𝑦)
The term out of the integral is called the Height of the Transfer Unit (HTU) and the integral the Number of
Transfer Units (NTU), thus the name HTU-NTU. These equations are coherent with the ones used by (Billet,
1995).
𝑢𝑥
𝐻𝑇𝑈𝑥 = (61)
𝑎𝑝ℎ ∙ 𝛽𝑥
𝑦𝑢 𝑥𝑢
𝑑𝑦 𝑑𝑥 (62)
𝑁𝑇𝑈𝑉 = ∫ 𝑁𝑇𝑈𝐿 = ∫
𝑦𝑜 (𝑦𝑒 − 𝑦) 𝑥𝑜 (𝑥𝑒 − 𝑥)
The overall 𝐻𝑇𝑈 is given by
𝐻𝑇𝑈𝑂𝑉 = 𝐻𝑇𝑈𝑉 + 𝜆 ∙ 𝐻𝑇𝑈𝐿 (63)
Where 𝜆 is called the stripping factor given by the quotient formed by the slopes of both curves, the
equilibrium and the operating curve.
𝑚𝑦𝑥
𝜆= (64)
𝐿
𝑉
Note that only one of the two curves is a straight line depending on the coordinate system used to represent
them. See Figure 16 center and right plots. If the absorption process is approximately linear, meaning that
both curves are approximately straight lines, this value will be constant across all the column.

Since the biogas absorption process is not linear, the evaluation of 𝜆 should consider the change of the slope
of the operating line throughout the columns height. It should be noticed that the integration for the NTU
value is done in the molar fraction coordinate system.
3.3.2 HTU calculation

To calculate the HTU term in Equations 59 and 60 the liquid and vapor loads, as well as the interfacial area,
were calculated in the fluid-dynamic description. The missing term is Higbie’s mass transfer coefficient. Most
of the equations presented in this subsection are based on (Billet, 1995) and (Billet & Schultes, 1999).
Liquid Phase Volumetric Mass Transfer Coefficient
For the liquid phase, in Equation 55 the residence time can be calculated as
ℎ𝑙 ∙ 𝑑ℎ
𝜏𝐿 = (65)
𝑢𝐿
Where 𝑑ℎ is the length of the flow path calculated as the hydraulic diameter
4∙𝜀
𝑑ℎ = (66)
𝑎
For the holding point, the holdup is calculated as in Equation 32. By inserting it in Equation 55 together with
Equation 65, the following expression is derived
1
2
1 𝐷𝐿 ∙ 𝑢𝐿𝑆 (67)
𝛽𝐿𝑆 = 2 ∙ ∙ 1
𝜋 2
12 𝜂 3 𝑎ℎ 3
( ∙ 𝑎2 ∙ 𝐿 ∙ 𝑢𝐿𝑆 ) ∙ ( ) ∙ 𝑑ℎ
( 𝑔 𝜌𝐿 𝑎 )
Rearranging
1
1 1 1 3
2 𝑔 𝜌𝐿 6 𝑢𝐿𝑆 3
1 𝐷𝐿 2 (68)
𝛽𝐿𝑆 = 1 ∙ ( ∙ ) ∙ ( ) ∙ ( ) ∙ (𝑎 )
12 𝜂𝐿 𝑎 𝑑ℎ ℎ
𝜋2 𝑎
Multiplying both sides by the interfacial area 𝑎𝑝ℎ
1
1 1 3
1
2 𝜌𝐿 6 3
2 𝐷𝐿 2 1 𝑎𝑝ℎ (69)
(𝛽𝐿 ∙ 𝑎𝑝ℎ )𝑆 = 1 1 ∙ (𝑔 ∙ ) ∙ 𝑢𝐿𝑆 ∙ 𝑎3 ∙ ( ) ∙ (𝑎 ) ∙
𝜂𝐿 𝑑ℎ ℎ 𝑎
𝜋2 ∙ 126 𝑎

According to (Billet & Schultes, 1999) experimental studies the volumetric mass transfer coefficient 𝛽𝐿 ∙ 𝑎𝑝ℎ
is adjusted to each packing by the introduction of a packing-dependent constant 𝐶𝐿
1
1 1 3
1
𝜌𝐿 6 3
2 𝐷𝐿 2 1 𝑎𝑝ℎ (70)
(𝛽𝐿 ∙ 𝑎𝑝ℎ )𝑆 = 𝐶𝐿 ∙ (𝑔 ∙ ) ∙ 𝑢𝐿𝑆 ∙ 𝑎3 ∙ ( ) ∙ ( 𝑎 ) ∙
𝜂𝐿 𝑑ℎ ℎ 𝑎
𝑎
1 1 1
In the constant the numeric term 2⁄(𝜋 2 ∙ 126 ) is included. Note that the numeric value 126 comes from the
liquid holdup at the holding point, but the rest of the term comes from the Higbie coefficient definition. To
1
apply the packing constant 𝐶𝐿 to any point in the operating intervals, the numeric value 126 must be
reintroduced in the expression. In general, by inserting Equation 65 in Equation 55
1
1 𝐷𝐿 ∙ 𝑢𝐿 2 (71)
𝛽𝐿𝑆 =2∙( ∙ )
𝜋 ℎ𝑙 ∙ 𝑑ℎ
Using the definition of the average liquid velocity given in Equation 25, introducing the packing constant 𝐶𝐿 ,
and multiplying both sides by 𝑎𝑝ℎ
1
1 𝐷𝐿 ∙ 𝑢
̅̅̅𝐿 2 𝑎𝑝ℎ (72)
𝛽𝐿 ∙ 𝑎𝑝ℎ = 𝐶𝐿 ∙ 126 ∙( ) ∙𝑎∙
𝑑ℎ 𝑎
By replacing Equation 72 in 61 gives
1
𝑢𝐿 1 1 𝑑ℎ 2 𝑢𝐿 1
𝐻𝑇𝑈𝐿 = = ∙ 12− 6 ∙ ( ) ∙ ∙ 𝑎 (73)
𝑎𝑝ℎ ∙ 𝛽𝐿 𝐶𝐿 𝐷𝐿 ∙ 𝑢
̅̅̅𝐿 𝑎 ( 𝑝ℎ )
𝑎
Vapor Phase Volumetric Mass Transfer Coefficient
For the vapor phase, in Equation 55 the residence time can be calculated as
(𝜀 − ℎ𝑙) ∙ 𝑑ℎ
𝜏𝑉 = (74)
𝑢𝑉
Introducing Equation 74 in 55
1
2 𝐷𝑉 ∙ 𝑢𝑉 2
𝛽𝑉 = 1 ∙ ( ) (75)
(𝜀 − ℎ𝑙) ∙ 𝑑ℎ
𝜋2

Inserting additional terms to write the equation as a function of dimensionless numbers
1 1
2𝐷𝑉 ∙ 𝑢𝑉 2 𝐷𝑉 𝜌𝑉 𝜂𝑉 𝑎 2 𝑎
𝛽𝑉 ∙ 𝑎𝑝ℎ = 1∙( ) ∙( ∙ ∙ ∙ ) ∙ ∙ 𝑎𝑝ℎ (76)
(𝜀 − ℎ𝑙) ∙ 𝑑ℎ 𝐷𝑉 𝜌𝑉 𝜂𝑉 𝑎 𝑎
𝜋 2
Rearranging
3 1 1
2 𝑎2 1
𝑢𝑉 ∙ 𝜌𝑉 2 𝜂𝑉 2 𝑎𝑝ℎ
𝛽𝑉 ∙ 𝑎𝑝ℎ = 1∙ 3∙ 1 ∙ 𝐷𝑉 ∙ ( 𝑎 ∙ 𝜂 ) ∙ (𝜌 ∙ 𝐷 ) ∙ 𝑎 (77)
𝜋 2 𝑑2 (𝜀 − ℎ𝑙)2 𝑉 𝑉 𝑉
ℎ
Reynolds and Schmidt numbers for the vapor phase can be defined as
𝑢𝑉 ∙ 𝜌𝑉
𝑅𝑒 = (78)
𝑎 ∙ 𝜂𝑉
𝜂𝑉
𝑆𝑐 = (79)
𝜌𝑉 ∙ 𝐷𝑉
Introducing the dimensionless numbers
3
1 1
2 𝑎2 1 2 2
𝑎𝑝ℎ
𝛽𝑉 ∙ 𝑎𝑝ℎ = 1∙ 3∙ 1 ∙ 𝐷𝑉 ∙ 𝑅𝑒𝑣 ∙ 𝑆𝑐𝑣 ∙ (80)
𝑎
𝜋 2 𝑑2 (𝜀 − ℎ𝑙)2
ℎ
Introducing the packing-dependent constant and adjusting the exponents in the 𝑅𝑒 and 𝑆𝑐 numbers
3
3 1
𝑎2 1 4 3
𝑎𝑝ℎ
𝛽𝑉 ∙ 𝑎𝑝ℎ = 𝐶𝑉 ∙ 3∙ 1 ∙ 𝐷𝑉 ∙ 𝑅𝑒𝑣 ∙ 𝑆𝑐𝑣 ∙ (81)
𝑎
𝑑ℎ2 (𝜀 − ℎ𝑙)2
Note that the exponents of the dimensionless numbers do not affect the units of the equation. The exponent
values, as well as the packing constant, are defined by (Billet & Schultes, 1999) experimental studies.
Replacing Equation 82 in 61 gives
3 1
3
𝑢𝑉 1 𝑑ℎ2 1 𝑎 ∙ 𝜂𝑉 4 𝜌𝑉 ∙ 𝐷𝑉 3 1
𝐻𝑇𝑈𝑉 = = ∙ 3 ∙ 𝑢𝑉 ∙ (𝜀 − ℎ𝑙)2 ∙ 𝐷𝑉 ∙ ( ) ∙( ) ∙ 𝑎 (82)
𝑎𝑝ℎ ∙ 𝛽𝑉 𝐶𝑉 𝑢𝑉 ∙ 𝜌𝑉 𝜂𝑉 𝑝ℎ
( 𝑎 )
𝑎2
Interfacial Area
The only term missing to calculate is the interfacial area per packed area 𝑎𝑝ℎ ⁄𝑎. This area relates to the area
where both phases make contact and thus transfer mass. According to (Billet & Schultes, 1999) this ratio can
be calculated depending on the operating interval.

For the interval between no load and the holding point as
0.75 −0.45
𝑎𝑝ℎ −
1 𝑢𝐿 ∙ 𝑑ℎ ∙ 𝜌𝐿 −0.2 𝑢𝐿2 ∙ 𝜌𝐿 ∙ 𝑑ℎ 𝑢𝐿2
= 1.5 ∙ (𝑎 ∙ 𝑑ℎ ) ∙ (
2 ) ∙( ) ∙( ) (83)
𝑎 𝜂𝐿 𝜎𝐿 𝑔 ∙ 𝑑ℎ
For the holding point as
0.75 −0.45
𝑎𝑝ℎ𝑆 −
1 𝑢𝐿𝑆 ∙ 𝑑ℎ ∙ 𝜌𝐿 −0.2 𝑢𝐿𝑆
2
∙ 𝜌𝐿 ∙ 𝑑ℎ 2
𝑢𝐿𝑆
(𝑎
= 1.5 ∙ ∙ 𝑑ℎ ) 2 ∙( ) ∙( ) ∙( ) (84)
𝑎 𝜂𝐿 𝜎𝐿 𝑔 ∙ 𝑑ℎ
For the interval between the loading point and the flooding point as
𝑎𝑝ℎ 𝑎𝑝ℎ𝑠 𝑎𝑝ℎ𝐹𝑙 𝑎𝑝ℎ𝑠 𝑢𝑉 13

= +( − )∙( ) (85)
𝑎 𝑎 𝑎 𝑎 𝑢𝑉𝐹𝑙
For the flooding point as
0.75 −0.45
𝑎𝑝ℎ𝐹𝑙 𝜎𝐿 0.56 1 𝑢𝐿𝐹 ∙ 𝑑ℎ ∙ 𝜌𝐿 −0.2 𝑢𝐿𝐹
2
∙ 𝜌𝐿 ∙ 𝑑ℎ 2
𝑢𝐿𝐹
= 10.5 ∙ ( ) ∙ (𝑎 ∙ 𝑑ℎ )− 2 ∙ ( ) ∙( ) ∙( ) (86)
𝑎 𝜎𝑊 𝜂𝐿 𝜎𝐿 𝑔 ∙ 𝑑ℎ
For the case of water scrubbing the surface tension of the aqueous phase and the one for water are assumed
to be equal, making the term (𝜎𝐿 ⁄𝜎𝑊 )0.56 equal to one.
Notice that the following terms are all included in the interfacial area calculations, and all of them are
dimensionless values.
𝑢𝐿 ∙ 𝑑ℎ ∙ 𝜌𝐿 𝑢𝐿2 ∙ 𝜌𝐿 ∙ 𝑑ℎ 𝑢𝐿2
= 𝑅𝑒 = 𝑊𝑒 = 𝐹𝑟 (87)
𝜂𝐿 𝜎𝐿 𝑔 ∙ 𝑑ℎ
Where 𝑊𝑒 is the Weber number and 𝐹𝑟 the Froude number
3.3.3 NTU calculation

To calculate the NTU, it is necessary to know the equilibrium values at the interface. Replacing equilibrium
values calculated in Equations 21 and 22 in 62
𝑦𝑢 𝑥𝑢
𝑑𝑦 𝑑𝑥
𝑁𝑇𝑈𝑉 = ∫ 𝑁𝑇𝑈𝐿 = ∫
(𝑥 ∙ 𝑚𝑦𝑥 − 𝑦) 𝑦 (88)
𝑦𝑜 𝑥𝑜 (𝑚 − 𝑥)
𝑦𝑥
The operating line in terms of molar fractions is not a linear function as it can be seen from Equation 12
𝐿 𝑥
[𝑌𝑢2 − 𝑉 ∙ (𝑋𝑢2 − 1 + 𝑥 )] 𝑓(𝑥)
𝑦= = (89)
𝐿 𝑥 𝑔(𝑥)
{1 + [𝑌𝑢2 − 𝑉 ∙ (𝑋𝑢2 − 1 + 𝑥 )]}

1 𝑦
[𝑋𝑢2 − 𝐿 ∙ (𝑌𝑢2 − 1 + 𝑦)]
( ) 𝑓(𝑦)
𝑥= 𝑉 = (90)
𝑔(𝑦)
1 𝑦
{1 + [𝑋𝑢2 − 𝐿 ∙ (𝑌𝑢2 − 1 + 𝑦)]}
(𝑉 )
Inserting in Equation 88
𝑥𝑢 𝑔(𝑥) ∙ 𝑚𝑦𝑥 ∙ 𝑑𝑥
𝑁𝑇𝑈𝐿 = ∫ (91)
𝑥𝑜 𝑓(𝑥) − 𝑥 ∙ 𝑔(𝑥) ∙ 𝑚𝑦𝑥
𝑦𝑢
𝑔(𝑦) ∙ 𝑑𝑦
𝑁𝑇𝑈𝑉 = ∫ (92)
𝑦𝑜 𝑓(𝑦) ∙ 𝑚𝑦𝑥 − 𝑔(𝑦) ∙ 𝑦
Note that the denominator is a quadratic function and the numerator is a straight-line function. An
alternative to solve these integrals is by using numerical integration.
3.3.4 Height Calculation Remark

The height of the scrubber is a sensitive parameter that can vary significantly with a small change in the
composition parameters. Since the absorption process is not linear, the changes in the composition will affect
the height depending on how close the concentrations of the outflowing liquid are to those of equilibrium.
The closer those two concentrations are, the greater the change in height is for a differential change in the
concentrations.
This sensitivity can be visualized using an example. In Figure 22 the height of a given column is plotted against
the upgraded biogas CH4 concentration. In the present example, given the fact that the concentration
saturation limit is 0.9502, notice how the height growth is asymptotical.
20
18
16 0.95; 17.28
Height of Scrubber [m]
14
12
10
8 0.94; 8.47
6
0.93; 6.87
4
0.91; 5.15 0.92; 5.87
2 0.9; 4.6
0.85; 2.95
0
0.84 0.86 0.88 0.9 0.92 0.94 0.96
Upgraded CH4 concentration [mol/mol]
Figure 22 Example of the height calculation while varying the composition of the upgraded biogas. Notice the non-
linearity of the function.

3.4 Fluid Properties Calculation

The fluid properties used in the calculations are dynamic viscosity, density, diffusivity, surface tension, and
solubility through Henry ‘s constant. The calculation of each of these variables for the mixtures requires itself
a complete study. Some of the calculations are based in recent studies like “A new model for the accurate
calculation of natural gas viscosity” by (Xiaohong, et al., 2017).
The pure substance properties like Molecular weight, critical temperature, and acentric value are obtained
from (Cheguide, 2016b) which is a compilation of values obtained from Dortmund Data Bank in (Dortmund
Data Bank, s.f.) and Cheric in (Cheric. Chemical Engineering and Materials Research Information Center, s.f.)
3.4.1 Dynamic Viscosity

The dynamic viscosity of the vapor phase is calculated at each slice according to the mixture composition.
The validity of the application of the mentioned method should be checked since, for high concentrations of
CO2, the composition ranges of the mixture are in the extremes reported by the authors.
The dynamic viscosity of the vapor is calculated according to (Xiaohong, et al., 2017) as
1 −0.551+(0.621+0.172∙𝑇𝑟 )∙𝜌𝑟1.273
𝜂𝑉 = 𝜂𝑉𝐵 ∙ (𝑇𝑟 )2 ∙ 𝑒
[
𝑇𝑟
] (93)
Where 𝑇𝑟 and 𝜌𝑟 are the reduced temperature and reduced density of the mixture given by
𝜌
𝜌𝑟 = (94)
∑𝑛𝑖=1 𝜌𝑐𝑖 ∙ 𝑦𝑖
𝑇
𝑇𝑟 = (95)
∑𝑛𝑖=1 𝑇𝑐𝑖 ∙ 𝑦𝑖
Where 𝜌 and 𝑇 are the density and temperature of the mixture, 𝜌𝑐𝑖 and 𝑇𝑐𝑖 are the critical density and critical
temperature of the component “i” of the mixture, and 𝑛 the total number of components of the mixture.
The base dynamic viscosity value 𝜂𝑉𝐵 is calculated as
𝑛 1
𝜂𝑉𝐵 = 3.142 ∙ ∑ 𝑀𝑖2 ∙ 𝑦𝑖 (96)
𝑖=1
Where 𝑀𝑖 is the molecular weight of each component of the mixture.

For the viscosity of the liquid phase, the tool uses the value for water reported in tables by (Harvey, 1998)
The influence of the diluted CO2 and CH4 is neglected, and the author of the present study has no information
on how the presence of these dissolved species might affect the calculated value.
3.4.2 Density
The density of the vapor mixture is calculated using Peng-Robinson modified equation with mixing rules as
𝑅∙𝑇 𝑎∙𝜑
𝑝= − (97)
𝑣̅ − 𝑏 𝑣̅ ∙ + 𝑏) + 𝑏 ∙ (𝑣̅ − 𝑏)
(𝑣̅

Alternatively, expressed as the general equation of state for real gases
𝑧∙𝑅∙𝑇
𝑝 ∙ 𝑣̅ = (98)
𝑀
Where 𝑍 is the compressibility factor given by
𝑍 3 − (1 − 𝐵) ∙ 𝑍 2 + (𝐴 − 2 ∙ 𝐵 − 3 ∙ 𝐵2 ) ∙ 𝑍 − (𝐴 ∙ 𝐵 − 𝐵2 − 𝐵3 ) = 0 (99)
Where the term 𝐴 is given by
𝜑∙𝑎∙𝑝
𝐴= (100)
𝑅2 ∙ 𝑇 2
The terms 𝐵 is given by
𝑏∙𝑝
𝐵= (101)
𝑅∙𝑇
The term 𝑎 for pure substances is given by
𝑅 2 ∙ 𝑇𝑐2
𝑎 = 0.45724 (102)
𝑝𝑐
The term 𝑏 for pure substances is given by
𝑅 ∙ 𝑇𝑐
𝑏 = 0.07780 (103)
𝑝𝑐
The term 𝜑 is given by
2
1
2) 2 (104)
𝜑 = [1 + (0.37464 + 1.54226 ∙ 𝜔 − 0.26992 ∙ 𝜔 ∙ (1 − (𝑇𝑟 ))]
Where 𝜔 is the acentric factor of the substance.

Since the equation of state is not for a pure substance, it is necessary to apply mixing rules. The term 𝑎
identified with sub-index m, referring to the mix, is calculated as
𝑛 𝑛
1
𝑎𝑚 = ∑ ∑ 𝑦𝑖 ∙ 𝑦𝑗 ∙ (𝜑𝑖 𝑎𝑖 ∙ 𝜑𝑗 𝑎𝑗 )2 ∙ (1 − 𝑘𝑖𝑗 ) (105)
𝑖=1 𝑗=1
Where 𝑦𝑖 and 𝑦𝑗 are the molar fractions of component 𝑖 or 𝑗 in the mixture, and 𝑘𝑖𝑗 is the binary interaction
parameter, which reflects the interaction between molecules of component 𝑖 with molecules of
component 𝑗.
Similarly, the term 𝑏 is calculated according to

𝑏𝑚 = ∑ 𝑦𝑖 ∙ 𝑏𝑖 (106)
𝑖=1
The binary interaction factor kij is fitted using laboratory data from (Rearmer, et al., 1944), the results of the
compressibility factor had a maximum deviation of 0.49% compared to those reported in the mentioned
source. The value for 𝑘𝑖𝑗 is 0.20461. The fitting process is developed following the proposed method by
(Cheguide, 2016)
The density of the liquid phase is calculated using the density of water as a base parameter. The value is
corrected assuming that the volume of the liquid does not change with the absorption of CO2 and CH4. The
mass is updated with the values calculated of the dissolved CH4 and CO2. The water density used as the base
parameter is calculated using interpolation with reported values from (Harvey, 1998).
3.4.3 Diffusivity
The diffusivity property is calculated following the work of (Budzianowski & Brodacka, 2017) which is taken
from specific studies for the diffusivity of CO2 and CH4 in water at high pressures. These correlations are
expected to have better accuracy than values calculated general diffusion coefficients by implementing the
Hayduk–Laudie correlation for non-electrolytes and small molecules, or the Nernst–Haskell equation for
electrolytes in the absence of an electric field (Crittenden, et al., 2012).
The diffusivity of CO2 in the liquid phase is calculated by
2119
𝐷𝐿2 = 2.35 × 10−6 ∙ 𝑒 − 𝑇 (107)
The diffusivity of CO2 in the vapor phase is calculated by
𝑇 1.75
𝐷𝑉2 = 7.84 × 10−5 ∙ (108)
𝑝
The diffusivity of CH4 in the liquid phase is calculated by
1.8769
𝑇
𝐷𝐿4 = 15.95 × 10−9 ∙ ( − 1) (109)
229.8
The diffusivity of CH4 in the vapor phase is calculated by
𝑇 1.5
𝐷𝑉4 = 4.29 × 10−4 ∙ (110)
𝑝
3.4.4 Surface Tension

The surface tension used is the one reported for water and is calculated according to the IAPWS-IF97 method
found in (Wagner & Kretzschmar, 2008) given by

1.256
(647.096 − 𝑇) (647.096 − 𝑇)
𝜎 = 0.2358 ∙ [ ] ∙ [1 − 0.625 ∙ ] (111)
647.096 647.096
Where 𝑇 is the temperature of the water given in Kelvin. The units of the surface tension are [𝑁⁄𝑚]. The
influence of CH4 and CO2 diluted in the liquid phase is neglected, and the author of the present study ignores
how the surface tension might be affected by the presence of these dissolved species. Nevertheless, the
surface tension is only used to calculate the interfacial area, and its influence is most important for flow
regimes where the inversion point has not been reached (Billet, 1995) which is not the case of biogas
upgrading.
3.4.5 Solubility
The Henry constant was described in detail in Subsection 3.1.2 “Equilibrium curve” on page 43.

4 Upgrading Cycle Calculation

High-pressure water absorption technique has the disadvantage of having a relatively high slip. The slip is
proportional to the operating pressure and inversely proportional to the operating temperature. One
standard way of reducing the slip is by introducing a flash column (tank) as depicted in Figure 8 and Figure 23
that is a simplified version.
Figure 23 High-pressure water upgrading cycle with a flash tank and stripper.
The following assumption will be used to set a framework:

• Water vapor is neglected.
• There is no pressure drop in the columns.
• The temperatures are constant and homogeneous in each element.
• There is perfect phase separation, meaning no entrainment.
• The flash tank operates at equilibrium.
• The CH4 concentration at the outlet of the absorption column is modeled using the combined model
described in Subsection 4.2.
• The mixing of streams is isothermal.
• The Raw biogas (RB) composition is known and given as a molar fraction.
• The upgraded biogas (Vo) is either a target or known.
• The composition of biogas is assumed to be only CH4 and CO2.
• Water is pure water. The only dissolved species are CO2 and CH4.
• The concentration of CO2 in the incoming water of the scrubber is known and constant equal to the
equilibrium concentration between water and atmospheric CO2 at the ambient conditions.
• The behavior of the vapor phase is modeled using the Peng-Robinson equation of state for binary
mixes. The interaction coefficient 𝑘𝑖𝑗 was found by curve fitting using laboratory reported data. See
Subsection 3.4.2.
• All models are steady state.

Since the stripper is not the focus of the present study, its presence in the cycle is not evaluated. It is
considered that it can always supply water at a concentration close enough to the equilibrium
concentration with atmospheric CO2. Because of this, the focus will be centered on the process depicted
in Figure 24. In the figure, as well that in the rest of the document, the variables that have no sub-index
referring to mass or volume are in molar flow units. 𝑁 is the vapor molar flow result of the flash process
that is recycled into the scrubber.
Figure 24. Simplified process omitting the stripper.
The present section is the product of the author of the present study by adapting and combining the works
of (Billet, 1995) and (Budzianowski, et al., 2017). Where relevant, citations and references will be given.
4.1 Mass Balances

Process Mass Balance
The general mass balance of the process for CO2 and CH4 is
𝑅𝐵2 + 𝐿 ∙ 𝑋𝑜2 = 𝑉𝑜2 + 𝐿 ∙ 𝑋𝑓2 (112)
𝑅𝐵4 = 𝑉𝑜4 + 𝐿 ∙ 𝑋𝑓4 (113)
Note that the term 𝐿 ∙ 𝑋𝑓4 is the slip of the system
𝑅𝐵4 − 𝑉𝑜4 = 𝐿 ∙ 𝑋𝑓4 = 𝑠𝑙𝑖𝑝 (114)
𝑅𝐵4 − 𝑉𝑜4 𝐿 ∙ 𝑋𝑓4 𝑠𝑙𝑖𝑝

= = = 𝑠𝑓 (115)
𝑅𝐵4 𝑅𝐵4 𝑅𝐵4
The amount of CO2 that will be removed by the system is the term 𝐿 ∙ 𝑋𝑓2 . It is important to notice that the
restricting flow is the liquid phase flow of the flash tank 𝐿 ∙ 𝑋𝑓 .

The slip defines the upgraded flow 𝑉𝑜4
𝑉𝑜4 = 𝑉𝑢4 − 𝑠𝑙𝑖𝑝 (116)
There is a relation between 𝑉𝑜4 and 𝑉𝑜2
𝑉𝑜2 𝑦𝑜2
𝑦𝑜2 = ∴ 𝑉𝑜2 = 𝑉𝑜4 = 𝑉𝑜4 ∙ 𝑌𝑜2 (117)
𝑉𝑜2 + 𝑉𝑜4 1 − 𝑦𝑜2
Scrubber Mass Balance
The mass balance for the scrubber is given in Equation 4. Explicitly, for CO2 and CH4 is given by
𝐿 ∙ (𝑋𝑢2 − 𝑋𝑜2 ) = 𝑉𝑢2 − 𝑉𝑜2 = 𝑉𝑢 ∙ 𝑦𝑢2 − 𝑉𝑜 ∙ 𝑦𝑜2 (118)
𝐿 ∙ 𝑋𝑢4 = 𝑉𝑢4 − 𝑉𝑜4 = 𝑉𝑢 ∙ 𝑦𝑢4 − 𝑉𝑜 ∙ 𝑦𝑜4 (119)
Note that it is not possible to express the slip in terms of these variables, since
𝑉𝑢 = 𝑅𝐵 + 𝑁 (120)
Notice that the slip is defined as a fraction of the incoming biogas flow in the system, and that 𝑉𝑢 is the sum
of this incoming biogas and the recirculation from the flash tank.
The reduction of the slip is achieved by reducing the partial pressure of CH4 at the inlet of the scrubber by
recirculating a mixture richer in CO2 than CH4 from the flash tank.
Flash Tank Mass Balance
The mass balance for the flash tank is
𝐿 ∙ 𝑋𝑢2 = 𝐿 ∙ 𝑋𝑓2 + 𝑁2 (121)

𝐿 ∙ 𝑋𝑢4 = 𝐿 ∙ 𝑋𝑓4 + 𝑁4 (122)
4.2 CH4 Absorption Model

Since the CH4 absorbed in the water changes the value of the molar flow of CH4, and this value is used to
calculate the CO2 mass transfer in the scrubbing model, there is a double interaction between the mass
transfer of both to the liquid phase. To avoid this closed equation system, an absorption model for CH4 is
used instead. The absorption model presented here is proposed by the author of the present study.
It is assumed that when the water enters the scrubber, the outgoing vapor is expected to have a high
concentration of CH4. This high concentration will cause a high mass transfer of CH4 from the up-flowing
vapor to the down-flowing liquid. As the liquid continues to flow, it gets exposed to lower CH4 concentration
vapor. The CH4 dissolved in the liquid will eventually saturate the liquid to the point that the mass-transfer
could be reversed as shown in Figure 25.

Figure 25 Qualitative description of the CH4 mass transfer behavior as a function of the height of the column. Source
Author of the present study.
When the liquid exits the column, the bulk concentration of CH4 will be higher than the interface
concentration because the mass transfer was taken place from the liquid to the vapor phase. To account for
this concentration difference at the exit, the CH4 concentration in the liquid phase will be calculated as the
mean value between the following two concentrations:
• The equilibrium concentration using the molar fraction of the vapor phase as the reference value as
shown on the left side of Figure 26. The equilibrium concentration in the liquid phase is calculated
using Equation 16 by
𝑦𝑢4
𝑥𝑢4 = (123)
𝑚𝑦𝑥4
• The flash equilibrium with the concentration of CO2 in the liquid phase as a reference as graphically
shown on the right side graph of Figure 26.
Figure 26 Left: Equilibrium concentration. Right: Flash equilibrium CH4 concentration.
The CH4 concentration at a given CO2 concentration in the liquid that exits the scrubber will result in
∗ 1 − 𝑚𝑦𝑥𝑎2 ∙ 𝑥𝑢2
1 − 𝑦𝑢2
𝑥𝑢4 = = (124)
𝑚𝑦𝑥𝑎4 𝑚𝑦𝑥𝑎4
Notice that the calculated liquid molar fraction concentration is higher than the equilibrium concentration
∗ ∗
for the actual vapor molar fraction. Since 𝑦𝑢2 < 𝑦𝑢2 then 𝑦𝑢4 > 𝑦𝑢4 .

The absorption model, called “combined model” (CM) in this study is then the mean of both 𝑥𝑢4
∗
𝑦𝑢4 + 𝑦𝑢4 1 − 𝑚𝑦𝑥𝑎2 ∙ 𝑥𝑢2 + 𝑦𝑢4
𝑥𝑢4 = = (125)
2 ∙ 𝑚𝑦𝑥𝑎4 2 ∙ 𝑚𝑦𝑥𝑎4
Note that the behavior of CH4 in the scrubber is quantitatively unknown, and only the resulting concentration
of the water exiting the scrubber is calculated with Equation 125. To calculate the CH4 flow for any point in
the scrubber, a simplified approach is used. This flow is needed to solve for the height and diameter of the
scrubber. Nevertheless, it must be pointed out that the absorption of CH4 is much lower than the absorption
of CO2 thus the molar flow of CH4 is close to constant.
The CH4 flow is calculated assuming a fast mass transfer at the top of the column and a low mass transfer at
the bottom. This assumption is supported by the fact that at the top the concentration of CH4 is much higher
than the bottom. The total absorbed flow will be distributed along the column using the following expression:
(𝑦2 − 𝑦𝑜2 )3
𝑓𝑦 = 1 − (126)
(𝑦𝑢2 − 𝑦𝑜2 )3
Where 𝑦2 is the molar fraction concentration of CO2 at any given height in the column. The 𝑓𝑦 factor will
have a value of one at the top of the column where the numerator will become zero. The CH4 flow at any
given point can be calculated as
𝑉4 = 𝑉𝑢4 − 𝑓𝑦 ∙ 𝐿 ∙ 𝑥𝑢4 (127)
4.3 Flash Tank Model

The flash tank is considered to perform as an equilibrium process meaning that the CO2 and CH4 are in
equilibrium between the phases. This equilibrium can be modeled using Henry’s law. Rewriting the mass
balance equation for the flash tank
𝐿 ∙ (𝑋𝑢2 − 𝑋𝑓2 ) = 𝑁2 (128)
𝐿 ∙ (𝑋𝑢4 − 𝑋𝑓4 ) = 𝑁4 (129)
Dividing these two equations and adding the term (𝑁2 + 𝑁4 )⁄(𝑁2 + 𝑁4 )
(𝑋𝑢2 − 𝑋𝑓2 ) 𝑁2 (𝑁2 + 𝑁4 ) 𝑦𝑓2

= ∙ = (130)
(𝑋𝑢4 − 𝑋𝑓4 ) 𝑁4 (𝑁2 + 𝑁4 ) 𝑦𝑓4
Where 𝑦𝑓4 and 𝑦𝑓2 are the vapor molar fraction of CH4 and CO2 respectively in the vapor phase exiting the
flash tank. Notice that the equilibrium is written in terms of the molar load. The following simplification is
used to be able to solve the equation analytically in a simpler fashion. If the molar load tends to cero, then
the molar load and the molar fraction are approximately equal.
𝑋
= 𝑥 If 𝑋 → 0 then 𝑋 ≈ 𝑥 (131)
1+𝑋

This simplification allows writing Equation 130 using the equilibrium Equation 16 and the fact that 𝑦𝑓4 = 1 −
𝑦𝑓2 as
𝑦𝑓2
(𝑥𝑢2 − 𝑚 ) 𝑦𝑓2
𝑦𝑥𝑓2
= (132)
1 − 𝑦𝑓2 1 − 𝑦𝑓2
(𝑥𝑢4 − 𝑚 )
𝑦𝑥𝑓4
Introducing the CH4 absorption model for 𝑋𝑢4 as presented in Equation 125
𝑦𝑓2
(𝑥𝑢2 − 𝑚 ) 𝑦𝑓2
𝑦𝑥𝑓2
= (133)
1 − 𝑚𝑦𝑥𝑎2 ∙ 𝑥𝑢2 + 𝑦𝑢4 1 − 𝑦𝑓2 1 − 𝑦𝑓2
( − )
2 ∙ 𝑚𝑦𝑥𝑎4 𝑚𝑦𝑥𝑓4
Solving for 𝑦𝑓2 gives the vapor molar fraction composition of the recycled vapor into the column as a function
of the liquid CO2 molar concentration leaving the column. Rearranging Equation 132
2
𝑎 ∙ 𝑦𝑓2 − 𝑏 ∙ 𝑦𝑓2 + 𝑐 = 0 (134)
Making
𝑎 = 2 ∙ 𝑚𝑦𝑥𝑎4 ∙ (𝑚𝑦𝑥𝑓2 + 𝑚𝑦𝑥𝑓4 )

𝑏 = −𝑚𝑦𝑥𝑓2 ∙ [𝑚𝑦𝑥𝑓4 ∙ (1 − 𝑚𝑦𝑥𝑎2 ∙ 𝑥𝑢2 + 𝑦𝑢4 ) + 2 ∙ 𝑚𝑦𝑥𝑎4 ] − 2 ∙ 𝑚𝑦𝑥𝑎4 ∙ 𝑚𝑦𝑥𝑓4 (135)
∙ (1 + 𝑚𝑦𝑥𝑓2 ∙ 𝑥𝑢2 )
𝑐 = 2 ∙ 𝑚𝑦𝑥𝑎4 ∙ 𝑚𝑦𝑥𝑓4 ∙ 𝑚𝑦𝑥𝑓2 ∙ 𝑥𝑢2
The solution for 𝑦𝑓2 is
−𝑏 ± √𝑏 2 − 4 ∙ 𝑎 ∙ 𝑐 (136)
𝑦𝑓2 =
2∙𝑎
If the term (𝑏 2 − 4 ∙ 𝑎 ∙ 𝑐) is greater than zero, then there will be two solutions. The one with physical
meaning will be the one that satisfies
0 ≤ 𝑦𝑓2 < 1 (137)
Notice that 𝑦𝑓2 cannot equal one since Equation 130 will produce a division by zero.
4.4 Closed Loop Equation Solving Strategy

To solve for the internal variables of the system, to be able to calculate the height of the scrubber, it is
necessary to solve the recirculation problems presented by the return of mass from the flash tank to the inlet
of the scrubber and the slip dependency between the flash and the upgraded biogas

From Equation 118 follows that
𝑋𝑢2 = 𝑓(𝑋𝑜2 , 𝑉𝑢2 , 𝑉𝑜2 , 𝐿) (138)
According to Equation 120 𝑉𝑢2 is a function of the raw biogas flow and the recycled flow from the flash
𝑉𝑢2 = 𝑓(𝑅𝐵, 𝑁2 ) (139)
From Equation 128 it can be seen that𝑁2 is a function of 𝑋𝑢2 , 𝑋𝑓2 and 𝐿
𝑁2 = 𝑓(𝑋𝑢2 , 𝑋𝑓2 , 𝐿) (140)
Similarly, it can be shown that 𝑋f2 is function of 𝑋𝑢2 among other variables
𝑋𝑓2 = 𝑓(𝑋𝑢2 , 𝑚𝑦𝑥𝑎2 , 𝑚𝑦𝑥𝑎4 , 𝑚𝑦𝑥𝑓2 , 𝑚𝑦𝑥𝑓4 ) (141)
Replacing the 𝑁2 and 𝑉𝑢2 dependencies in Equation 138
𝑿𝒖𝟐 = 𝑓(𝑋𝑜2 , 𝑅𝐵, 𝑿𝒖𝟐 , 𝑚𝑦𝑥𝑎2 , 𝑚𝑦𝑥𝑎4 , 𝑚𝑦𝑥𝑓2 , 𝑚𝑦𝑥𝑓4 , 𝑉𝑜2 , 𝐿) (142)
In this first analysis, there is already a close loop dependency detected for 𝑿𝒖𝟐 .
According to Equation 117 𝑉𝑜2 is a function of 𝑉𝑜4 , and 𝑉𝑜4 is a function of the slip according to Equation 116
resulting in
𝑉o2 = 𝑓(𝑉u4 , 𝑠𝑙𝑖𝑝, 𝑦𝑜2 ) (143)
Since solving the flash equilibrium will determine the slip according to Equation 115, it can be shown that the
slip is a function of 𝑋𝑢2
𝑠𝑙𝑖𝑝 = 𝑓(𝑋𝑓4 , 𝐿) = 𝑓(𝑦𝑓4 , 𝑚𝑦𝑥𝑓4 , 𝐿) = 𝑓(𝑋𝑢2 , 𝑚𝑦𝑥𝑎2 , 𝑚𝑦𝑥𝑎4 , 𝑚𝑦𝑥𝑓2 , 𝑚𝑦𝑥𝑓4 , 𝐿) (144)
Replacing these dependencies given is found that
𝑉o2 = 𝑓(𝑉u4 , 𝑠𝑙𝑖𝑝, 𝑦𝑜2 ) = 𝑓(𝑉u4 , 𝑋𝑢2 , 𝑚𝑦𝑥𝑎2 , 𝑚𝑦𝑥𝑎4 , 𝑚𝑦𝑥𝑓2 , 𝑚𝑦𝑥𝑓4 , 𝐿, 𝑦𝑜2 ) (145)
Replacing Equation 145 in 142
𝑿𝒖𝟐 = 𝑓(𝑋𝑜2 , 𝑅𝐵, 𝑿𝒖𝟐 , 𝑚𝑦𝑥𝑎2 , 𝑚𝑦𝑥𝑎4 , 𝑚𝑦𝑥𝑓2 , 𝑚𝑦𝑥𝑓4 , 𝑉u4 , 𝑿𝒖𝟐 , 𝑦𝑜2 , 𝐿) (146)
The double closed loop relation needs to be solve keeping the mass balance and the solubilities equal to or
less than the equilibrium values.
The strategy implemented in this study to solve the double dependency is to guess a slip value. Then iterate
starting with zero recirculation until convergence in both loops is achieved within a residual stop criterion.
Typical values used in this study were between 10−14 and 10−10 for the stop criterion. Refer to section 6.3
on page 77 where the model implementation is presented.

5 Internal Energy Consumption

The high-pressure water-scrubbing technique requires auxiliary equipment as depicted in Figure 27 to
provide the adequate operating conditions.
Figure 27 High-pressure water upgrading cycle with auxiliary equipment highlighted.
The energy demand to operate each equipment is supplied by an external source or internally from the CHP
unit of the biogas system. The CHP can operate with either raw biogas or upgraded biogas. The difference
lies in the pretreatment the fuel must undergo to protect the internal combustion engine and infrastructure
in general. From an energy perspective, it is more efficient to use raw biogas to generate the electricity; this
is assuming that the internal combustion engine will perform with the same efficiency with the two fuels.
To calculate the power demand and energy consumption of the equipment simple energy equations are
used. The results provided by these serve as a guide or reference point to the real power and energy needs.
Each equipment is analyzed in the following subsections.
This section is mainly based on (Budzianowski, et al., 2017).
5.1 Compressor
The compressor increases the pressure of the incoming flow of raw biogas and the recycled flow from the
flash tank up to the operating point of the absorption column. A key parameter to define is the number of
stages needed to perform the task. To calculate this number, the pressure ratio between the inlet and outlet
of the gas from each stage, —called the inter-stage compression factor 𝐶𝐹— must be kept under four.
Keeping the 𝐶𝐹 under 4, avoids high discharge temperatures protecting the machine and preventing
unwanted effects like oil and biogas degradation (Hanlon, 2001).
The number of stages is determined by
𝑝 ∙𝑝
𝑙𝑜𝑔 ( 𝑎𝑝 𝑜𝑣 )
𝑎𝑡𝑚 (147)
𝑛 = 𝑖𝑛𝑡𝑒𝑔𝑒𝑟 ( )+1
𝑙𝑜𝑔(𝐶𝐹)

Where 𝑝𝑎 is the operative absorption column pressure, and 𝑝𝑎𝑡𝑚 is the atmospheric pressure.
The value 𝑝𝑜𝑣 accounts for the overpressure needed to overcome the pressure losses upstream of the
column.
Once the number of stages is set, the operative inter-stage compression factor 𝐶𝐹𝑜𝑝 is calculated
1
𝑃𝑎 ∙ 𝑃𝑜𝑣 𝑛 (148)
𝐶𝐹𝑜𝑝 =( )
𝑃𝑎𝑡𝑚
According to (Budzianowski, et al., 2017) the compression power for stage “𝑥” is given by
𝑘 𝑝𝑑𝑖𝑠
𝑉𝑚𝑜𝑙 ∙ 𝑅 ∙ 𝑇 ∙ ∙ ) − 1]
𝑘 − 1 [(𝑝𝑠𝑢𝑐 (149)
𝑃𝑥 =
𝜂𝐶𝑖𝑠 ∙ 𝜂𝐶𝑚𝑒𝑐
Where 𝑉𝑚𝑜𝑙 is the molar flow of biogas, 𝑅 is the universal gas constant, 𝑇 is the suction temperature, 𝑘 =
𝑐𝑝 ⁄𝑐𝑣 where 𝑐𝑝 and 𝑐𝑣 are the specific heat values of the biogas vapor mix at constant pressure and constant
volume respectively, 𝜂𝐶𝑖𝑠 and 𝜂𝐶𝑚𝑒𝑐 are the isentropic and mechanic efficiencies of the compressor
respectively.
In this study, it is assumed that the flow for each stage of the compressor is optimized in the sense that the
flow recycled from the flash tank will enter at the optimal stage. This concept translates in that 𝑉𝑚𝑜𝑙 depends
on the molar flow that enters the stage in question. If there is more than one stage, then the recycled flow
will enter the compressor at the stage where the suction pressure is lower than the flash pressure and the
discharge pressure is higher than the flash pressure. For example, for the first stage, the flow will be the raw
biogas and the recycled gas coming from the flash tank if the pressure of the flash tank is lower than the
discharge pressure of the first stage.
The total power will be the sum of the power of each stage
𝑛
(150)
𝑃𝐶𝑏𝑔 = ∑ 𝑃𝑥
𝑛=1
Where 𝑃𝐶𝑏𝑔 is the power to run the compressor.
5.2 Coolers
After compressing the biogas or after the stripping process, the biogas and the water flows must undergo
cooling until the temperature reaches the operating temperature of the scrubber.
It is assumed that the compressor is fitted with a gas-to-air heat exchanger and that the compressed raw
biogas will exit the unit at ambient temperature plus an over temperature 𝑇𝑜𝑣 . This overtemperature is
considered normal between 5 and 15°C, higher overtemperatures are a sign of either problems in the heat
exchanger or a heat exchanger too small for the task.
Regardless of the common practices to cool the interstage flow, it is possible to have a gas-to-liquid heat
exchanger and use the rejected heat, for example, to heat up the digester.

For the temperature of the water exiting the stripper, is considered that the column acts as a heat exchanger
where water and air will reach equilibrium temperature given by
𝑉𝑚𝑎𝑠𝑎𝑖𝑟 ∙ 𝑐𝑝𝑎𝑖𝑟 ∙ 𝑇𝑎𝑡𝑚 + 𝐿𝑚𝑎𝑠 ∙ 𝑐𝑝𝐿 ∙ 𝑇𝑓 (151)

𝑇𝑠 =
𝑉𝑚𝑎𝑠𝑎𝑖𝑟 ∙ 𝑐𝑝𝑎𝑖𝑟 + 𝐿𝑚𝑎𝑠 ∙ 𝑐𝑝𝐿
Where 𝑉𝑚𝑎𝑠𝑎𝑖𝑟 is the mass flow of air, and 𝑇𝑓 is the flash operating temperature.
It is possible that the real temperature would be lower than the calculated one since the water will evaporate
inside the stripper removing heat and thus lowering its temperature, and because the column acts like a
counterflow heat exchanger.
From the discharge temperature of the compressor unit, the biogas flow must be cooled to the operating
temperature of the column. The rejected heat is given by
𝑉𝑚𝑎𝑠 ∙ 𝑐𝑝 ∙ [𝑇𝑎𝑡𝑚 + 𝑇𝑜𝑣 − (𝑇𝑎 − 𝑇𝑎𝑑 )] (152)

𝑃𝐶𝑂𝑏𝑔 =
𝐶𝑂𝑃2
Where 𝑉𝑚𝑎𝑠 is the mass flow of biogas to cool, 𝑇𝑎 is the operative temperature of the column 𝑇𝑜𝑡 is the
overtemperature, 𝑇𝑎𝑑 is the additional temperature drop to compensate for heat gains from the cooler to
the column, and 𝐶𝑂𝑃2 is the coefficient of performance of the cooler system.
Similarly, the rejected heat for the liquid flow is calculated by
𝐿𝑚𝑎𝑠 ∙ 𝑐𝑝𝐿 ∙ [𝑇𝑠 − (𝑇𝑎 − 𝑇𝑎𝑑 )] (153)

𝑃𝐶𝑂𝐿𝐿 =
𝐶𝑂𝑃2
Where 𝑇𝑎𝑑 is the additional temperature drop needed to compensate for the heat gains from the cooler to
the scrubber. It must be noticed that the resulting liquid temperature must always be higher than the freezing
point. For this study a minimum resulting temperature of 2°C is set as limit.
5.3 Water Pump and Air Blower

The water pump is responsible for recirculating the water from the stripping column to the scrubbing column.
Since the pressure of the scrubber is higher than the flash tank’s pressure, the water will flow because of this
pressure difference. The same phenomenon occurs between the flash tank and the stripper.
The air blower increases the pressure of the stripping air to ensure that it can flow through the stripper.
An additional overpressure is introduced for both calculations to compensate for the pressure losses
between the blower and the stripper and between the pump and the scrubber.
The power needed to run the pump is given by
(𝑝𝑎 ∙ 𝑝𝑜𝑣 − 𝑝𝑎𝑡𝑚 ) ∙ 𝑉𝑣𝑜𝑙𝐿 (154)

𝑃𝑃 =
𝜂𝑃
Where 𝑝𝑎 is the operative pressure of the column, 𝑝𝑜𝑝 is the overpressure parameter, 𝑉𝑣𝑜𝑙𝐿 is the volumetric
flow of water, and 𝜂𝑃 is the efficiency of the pump.
The power demanded by the blower is
(𝑝𝑆 ∙ 𝑝𝑜𝑣 − 𝑝𝑎𝑡𝑚 ) ∙ 𝑉𝑣𝑜𝑙𝑎𝑖𝑟

𝑃𝐵 = (155)
𝜂𝐵

Where 𝑉𝑣𝑜𝑙𝑎𝑖𝑟 is the volumetric flow of air, 𝑝𝑆 the operative pressure of the stripper and 𝜂𝐵 the efficiency of
the blower.
5.4 Electricity Generator

The internal electricity consumption is assumed to be generated using an internal combustion engine
attached to an electric generator. To calculate the amount of biogas, either raw or upgraded, needed to
generate it is necessary to calculate the lower heating value (LHV) of the fuel as
𝑦4 ∙ 𝐿𝐻𝑉4 ∙ 𝑀4
𝐿𝐻𝑉𝑏𝑔 = (156)
𝑀𝑏𝑔
Where 𝐿𝐻𝑉4 is the LHV of pure methane equal to 50 000 𝑘𝐽⁄𝑘𝑔, 𝑦4 is the molar fraction of CH4 in the mix,
𝑀4 and 𝑀𝑏𝑔 are the molecular weight of CH4 and the biogas mix respectively.
The fuel required will be given by
𝑃𝐶 + 𝑃𝐶𝑂𝑏𝑔 + 𝑃𝐶𝑂𝐿 + 𝑃𝐵 + 𝑃𝑃
𝑉𝑚𝑎𝑠𝑏𝑔 = (157)
𝜂𝐺 ∙ 𝐿𝐻𝑉𝑏𝑔
Where 𝜂𝐺 is the efficiency of the generator set and 𝑉𝑚𝑎𝑠𝑏𝑔 is the mass flow of the biogas mix. Note that the
result of this calculation is a mass flow given in 𝑘𝑔⁄𝑠.
Efficiencies, Overpressures, Additional temperature
All the described parameters in the power calculations can be changed by the user of the modeling tool
according to specific applications of real data. The values reported in Table 6 are used to run the model and
serve only as examples, the values are not referred to any particular condition. Most of the values are taken
from (Budzianowski & Brodacka, 2017)
Table 6 Values of efficiencies, overpressure, additional temperature and others used in the power calculations. Source
Variable Description Value

𝑪𝑭 Inter-stage maximum compression factor 4.00
𝜼𝑪𝒊𝒔 Compressor isentropic efficiency 0.75
𝜼𝑪𝒎𝒆𝒄 Compressor mechanical efficiency 0.80
𝑻𝒐𝒗 Compressor heat exchangers inter-stage delta temperature 10.00
𝒑𝒐𝒗𝑪 Compressor overpressure 1.10
𝜼𝑷 Water pump efficiency 0.60
𝒑𝒐𝒗𝑷 Pump overpressure 1.15
𝜼𝑩 Air blower efficiency 0.60
𝒑𝒐𝒗𝑩 Blower overpressure 1.20
𝑪𝑶𝑷𝟐𝒃𝒈 Biogas cooler coefficient of performance 2 2.50
𝑻𝒐𝒗𝒃𝒈 Biogas additional temperature drop 5.00
𝑪𝑶𝑷𝟐𝑳 Watercooler Coefficient of performance 2 3.00
𝑻𝒐𝒗𝑳 Water additional temperature drop 3.00
𝜼𝑮 Generator unit efficiency 0.35

6 Model Implementation in VBA

A model in Microsoft® Excel used as the host of VBA was implemented to run as a self-standing tool to process
all the equations, conditions and other operation described in the previous sections.
There are several tasks to solve depending on the needs, for example, it is possible that the user will be
interested in calculating the height of a scrubber given any upgrading task. Another example is that the user
will be interested in calculating the concentrations and slip resulting of a given column operation varying
biogas flows, concentrations, pressure, and temperature among others. Alternatively, it may also be possible,
that the user is interested in knowing details of the flows inside the scrubber, like velocities, flooding point,
flow parameter, and the slope of the equilibrium curve among others.
The following section will describe the most important blocks coded in the developed modeling tool. The
combined use of these blocks can provide the answers to many of the questions and needs when modeling
an upgrading biogas system.
6.1 General Description of the Tool

The tool runs on a conventional excel workbook. It has a spreadsheet that acts as the user interface where
the user enters all variables and selects operating conditions. It also serves as the central reporting area as it
displays the most relevant results.
There are another three spreadsheets that act as databases where the tool picks information from. These
databases are left open, and the user can relate to them at any time. One of the databases contains the
properties of liquid water like density and dynamic viscosity. Another database contains the properties, like
molecular weight and critical temperature, of the used species in the calculations. The last database contains
the packing constants and properties, like area per packed volume and void fraction.
One last spreadsheet presents the detailed results of internal variables of the scrubbing column. As it will be
described further the model breaks the column in several slices, the result of the calculation for each slice is
reported in this spreadsheet.
6.2 User Interface

In Figure 28 a screenshot of the interface is presented. The user can set the operational variables like pressure
and temperature of the digester, scrubber, flash tank, stripper, and ambient. The tool allows the user to
choose if a flash tank is present or not. The flows, concentrations and column dimensions are either
calculated or entered by the user depending on the task.
To generate the internal electricity needs the user can select the energy source to use as fuel for the CHP
unit between raw and upgraded biogas; the user also has the option to select an external source meaning
that all the biogas would be upgraded and none would not be used to run the CHP unit. The resulting power
and energy analysis are displayed for the given task.
The slip is one of the most crucial variables that define the system, and it is always presented as a result for
every run of the model. The slip has triple importance, from the model perspective it is the limiting factor
located in the term 𝐿 ∙ 𝑋𝑓4 in the liquid at the outlet of the flash tank. From an energy perspective the slip
represents fuel lost, but to lower the slip the operative pressures of both, the scrubber and the flash tank
must be set at low values, meaning that it requires an energy analysis to determine the breakpoint at which

lowering further the slip value will demand more energy than the one saved from the slip as fuel. And from
an environmental and regulatory perspective, the slip must be kept to low values.
Figure 28 User Interface of the modeling tool developed. The interface has additional fields not shown in the figure.
The additional fields are where the packing material is selected, and the results of the scrubber are displayed like the
velocities of the vapor and liquid phases, the slope of the equilibrium curve, the liquid holdup, the loading and
flooding point loads among others.
The tasks the user can perform are:

• Calculate the minimum required liquid flow.
• Calculate the maximum limit of the upgrading concentration.
• Calculate the resulting upgrading concentration given the column’s dimensions.
• Calculate the suggested diameter.
• Calculate the height of the scrubbing column for an upgrading task.
• Calculate the slip for an upgrading task.
• Calculate the power and energy requirements for an upgrading task.
Since the code is open, there is the possibility to automatize routines to run a series of modeling cases. For
example, model a given system to operate at different pressures in the flash tank to evaluate the energy and
slip behavior.
6.3 Modeling Strategy

The general solution strategy to calculate any requested task is shown in Figure 29. In blue is highlighted the
solving block. There are two main solving blocks, one called “Loop block” that calculates all variables of the
upgrading cycle and performs the mass balance of the system. The other block, called “Scrubber block,”
calculates the dimensions of the scrubber and all the internal operating variables including the loading and
flooding points.
The Loop block has one additional block called the “Flash block” which is embedded in the Loop block. In
Figure 30 the Loop and Flash block are schematically presented. To solve the Loop block, it is necessary to

use the Flash Block. To find a solution to any given upgrading task, it is necessary to iterate over two
closed-loop set of equations, each of these described blocks solve one set each.
Figure 29 Modeling tool general block flow
For the first iteration of the Loop block, the slip is guessed, then the Flash block iterates until the recycled
flow converges. At that point, the resulting slip is compared to the guessed one, and if different, a new
iteration is carried out over the Loop block.
Figure 30 Loop block calculation strategy.
In some cases, there is no convergence because of low liquid flow, or low pressure, or high temperature, or
any combination that produces an impossible separation task. The method to update the slip between

iterations consists of making the next slip value equal to the one calculated from the solution from the Flash
block as
𝑠𝑓(𝑖) = 𝑠𝑓(𝑖−1) (158)
The first guess for the slip can be any positive value less than 25%. The selection does not change the results
nor changes the convergence time significantly. The method is relatively independent of this first guess.
The Flash block iterates over the recycled flow by updating the concentrations of the inflow of the scrubber.
It uses Equation 120 and the fact that
𝑉𝑢2 𝑅𝐵2 + 𝑁2
𝑦𝑢2 = = (159)
𝑉𝑢2 + 𝑉𝑢4 𝑅𝐵2 + 𝑁2 + 𝑅𝐵4 + 𝑁4
Replacing 𝑉𝑢2 and 𝑉𝑢4
𝑅𝐵2 + 𝑁2
𝑦𝑢2 = (160)
𝑅𝐵2 + 𝑁2 + 𝑅𝐵4 + 𝑁4
Note that the recycled flow 𝑁 has a higher CO2 content than the raw biogas incoming flow 𝑅𝐵.
Some of the common problems that impede convergence of the blocks are:
• The concentration of the dissolved CO2 or CH4 in the liquid is higher than the equilibrium
concentration.
• Flash quadratic equation returns values with no physical meaning, I.E., molar fractions over the unit
or negative values. These false physical solutions are often caused because of erroneous negative
concentrations found in the liquid phase. The cause is that one of the guessed values does not
represent a valid system configuration. Accordingly, the mass balance is only reached by negative
flows.
• Flash block does not converge due to low liquid flow. This problem is avoided by checking if there is
a valid solution with the given liquid flow by calculating the slip with the given values. This importance
of this calculation is to check the sign of the slip and not the absolute value. If the sign is negative,
then there is no solution with the given parameters.
The Scrubber block performs two core tasks, calculates NTU and HTU to produce the height. NTU depends
on concentrations while HTU depends on fluid dynamics. These dependencies are expected since to calculate
HTU, what governs the mass transfer coefficient is the residence time of the interface. This time depends on
the frequency at which the interface renews, which is a function of the type of flow, its velocities, and the
properties of the fluids in question. To calculate the NTU value, only the concentrations are used. See
Equation 88 on page 59.
The Scrubber block is presented in Figure 31. Since the concentrations of the phases change drastically in an
upgrading task, the density of the vapor phase and the ratio 𝐿/𝑉 also change considerably. If the column is
chopped into a series of columns, the change of the properties of the fluids reduce between the inlet and
the outlet of each slice as the size of the slice gets smaller. The slicing of the column is depicted in Figure 32.
It is important to point out that the density of CO2 is higher than the density of CH4. For example, at normal
conditions (0°C and 1 atm) the densities are 0.72 𝑘𝑔⁄𝑚3 for CH4 and 1.98 𝑘𝑔⁄𝑚3 for CO2.

Since CO2 is being transferred from the vapor to the liquid phase, the molar flow of the vapor phase decreases
while the molar flow of the liquid phase grows increasing the ratio 𝐿/𝑉. This ratio, influences both
calculations NTU and HTU. The influence in NTU is caused because the slope of the operation curve is the
𝐿/𝑉 ratio, which sets the variables 𝑥 and 𝑦 of the integrals given in Equation 62. The influence in the HTU is
given by Equation 63, where the ratio 𝐿/𝑉 is one of the variables used to calculate the stripping factor 𝜆.
Figure 31 Calculation strategy to solve for the height of the scrubber

Figure 32 Slicing of the column. Strategy for applying HTU-NTU method. Qualitative description of the density of the
vapor phase behavior in the column as a function of the height.
The slope of the operating curve can be calculated by performing differentiation of Equation 89. It is possible
to do a numerical differentiation using forward differencing at each slice as
𝑑𝑦 𝑓(𝑥 + Δ𝑥) − 𝑓(𝑥)

= 𝑓 ′ (𝑥) = (161)
𝑑𝑥 Δ𝑥
Applying to the slice 𝑖
𝐿 𝑦𝑢2_𝑖 − 𝑦𝑜2_𝑖
= 𝑓 ′ (𝑥) = (162)
𝑉 𝑥𝑢2_𝑖 − 𝑥𝑜2_𝑖
With the 𝐿/𝑉 slope, the stripping factor for the slice is calculated according to Equation 64. This value is
approximately equal to the relation presented by (Billet & Schultes, 1999)
𝑁𝑇𝑈𝐿
𝜆= (163)
𝑁𝑇𝑈𝑉
It was experienced that the results using Equation 163 converged using fewer slices than using Equation 162.
The number of slices reduced from 30 to 10 for changes in height smaller than 0.01 m.

7 Model Comparison
The performance of the model should be checked and validated. Ultimately, the validation should be done
using experimental data or the data from real scrubbing system operation. The scope of this study is limited
to the basic tool development that would serve as a platform for future testing and operation of IMBAB —
which has not yet started pilot operations—. Once IMBAB starts testing designs, the tool can be tested
against the real performance of the upgrading systems. There are several points where adjustment can be
performed like the exponent values of the dimensionless numbers Reynolds, Froude, and Schmidt, or the
exponent ”13” which relates the operation between the loading point and the flooding point in Equation 52.
For the present study, a comparison to check if the tool behaves coherently in a range of operation is
performed. The comparison will be developed between several cases ran in Aspen Plus and the developed
tool.
The comparison aims at testing two core models of the tool. The first model, called the Cycle model, performs
the calculation of all the flows of the cycle represented by the slip as the sensitive parameter. The second
model, called the Scrubber model, performs the calculation of the dimensions of the scrubber, represented
by the height of the scrubbing column. For the former feature, two approaches are used. The first one is to
set the height of the column and solve for concentrations, and the second one is to set the concentrations
and solve for the height.
7.1 General Framework for the Comparison

A set of runs are designed to perform the comparison. Three flows of raw biogas are the basis over which the
variation of parameters is done. Each of the flows is ran with and without the flash tank. The reason is that
the Scrubber model should be tested under the same flows in both models. If the flash is present, the inflow
to the scrubber is dependent on the recirculation from the flash. If the system has a slightly different flash
equilibrium solution, then the recirculation will also be different, and the differences in the heights or
concentrations out of the column will not correspond to the behavior of the models, but to the difference in
the setup.
Table 7 Structure of the comparison runs. The values of flow and "from" "to" are approximations of the values used.
RB: Raw biogas flow, Lo Liquid flow, pf: pressure of the flash tank, ps: pressure of the scrubber, Ts: temperature of the
scrubber, Hs: height of the scrubber.
RB Flow and Packing Flash Tank Variable From To Points
10 𝑁𝑚3 /ℎ - Pall ring 25 mm Yes 𝑅𝐵 0.5 ∙ 𝑅𝐵 3 ∙ 𝑅𝐵 11
50 𝑁𝑚3 /ℎ - Pall ring 35 mm No 𝐿𝑜 0.5 ∙ 𝐿𝑜 3 ∙ 𝐿𝑜 10
50 𝑁𝑚3 /ℎ - VSP ring 25 mm 𝑝𝑓 1.5 bar 6 bar 9
50 𝑁𝑚3 /ℎ - Rallu ring 50 mm 𝑝𝑆 4 bar 14 bar 6
100 𝑁𝑚3 /ℎ - Pall ring 35 mm 𝑇𝑆 4°C 20°C 10
𝐻𝑆 1m 8m 8
In Table 7 the design of the structure for the comparison is presented. At each run, only one variable in
question is changed leaving fixed all other parameters. For example, for the raw biogas variable run: The
liquid flow; the height, pressure, and temperature of the scrubber; the pressure of the flash tank; the raw
biogas concentrations, and the type of packing material are all fixed while only the raw biogas flow is varied.

The diameters of the columns are chosen using the nominal run for each variable. The selection corresponds
to the diameter where the vapor velocity is 60% of the vapor velocity at the flooding point. This methodology
of diameter selection is applied following the work of (Budzianowski & Brodacka, 2017).
Cycle Model comparison
When solving a cycle, there are two options. The first option is to know the upgrading task, I.E., know the
inflows and the upgrading target concentrations, and solve for the height and slip. The second option is to
know the inflows and the height of a column and solve for the concentrations of the upgraded flow and the
slip.
Both options were tested to make the comparison. To test the first option, where the outlet concentrations
are known, the resulting concentrations of the model ran in Aspen Plus were used in the developed tool to
solve for height and slip. To test the second option, where the height is set, the same upgrading setup was
ran in the developed tool as in Aspen Plus.
Scrubber Model Comparison
For the Scrubber model, there are also two options as in the comparison of the Cycle model. In the case of
the Scrubber model, the flash tank is taken out of the cycle, and only the scrubber is modeled. The data for
this model is the same used in the Cycle model comparison. The inflows for the scrubber are taken from the
model ran in Aspen, I.E., the 𝑉𝑢 and 𝐿𝑜 flows, and the inlet and outlet concentrations.
Deviation Calculation Reporting Method
For both models the comparisons are made using Aspen as a basis, meaning that the slip, height, and
concentrations calculated by Aspen are the reference values. The slip deviations are calculated by
𝑠𝑓𝐴𝑠𝑝𝑒𝑛 − 𝑠𝑓𝑡𝑜𝑜𝑙
𝑠𝑓𝑑𝑒𝑣_𝑥 = (164)
𝑠𝑓𝐴𝑠𝑝𝑒𝑛
The height calculations from both models —even if it is not exactly a fair comparison for the Cycle model—,
are evaluated as
𝐻𝐴𝑠𝑝𝑒𝑛 − 𝐻𝑡𝑜𝑜𝑙
𝐻𝑑𝑒𝑣_𝑥 = (165)
𝐻𝐴𝑠𝑝𝑒𝑛
The concentrations deviations are evaluated using CH4 as a reference as
𝑦𝑜4_𝐴𝑠𝑝𝑒𝑛 − 𝑦𝑜4_𝑡𝑜𝑜𝑙
𝑦𝑜4_𝑑𝑒𝑣_𝑥 = (166)
𝑦𝑜4_𝐴𝑠𝑝𝑒𝑛
Where “𝑥" is either the Cycle model or the Scrubber model.
7.2 Aspen Model: Block and Streams Description

The model setup in Aspen is intended to be as close as possible to the setup of the developed tool. The block
distribution is shown in Figure 33. As already discussed, the stripper is not included in the model. As it was
assumed that it would perform as needed and that it processes the amount of the outflow liquid from the

flash tank, as well as it ensures a close-to-atmospheric-equilibrium CO2 concentration in the water that goes
back to the scrubber.
Figure 33 Block layout of the Aspen model. (Aspen Technology, Inc, 2017)
The properties of the species calculation method in the model is set to NTRL-RK (Non-Random Two-Liquid
Model–Redlich-Kwong equation of state) following the conclusions stated by (Cozma, et al., 2015). CH4 and
CO2 were modeled as “Henry components.”
The scrubber block was modeled using the “RadFrac distillation column” as it allows for rigorous calculations
using a rate-based model where the packing materials are defined. The column is set as an absorber column,
and no reboiler nor condenser are present. The number of stages was set to 10; it was found that since the
final simulation was “rate-based” this number of stages relates to the number of segments where Aspen runs
the integration and solves the mass-transfer problem and no the number of theoretical stages.
A packed section is defined, and the details of the packing are set. An important feature is to set the flow
model is to counter-current instead of Mixed (as default). The Billet method is selected to compute the
interfacial area as well as the modeling strategy for the mass transfer coefficients. The film is considered in
the calculations allowing to model the difference between the film and the bulk concentrations. The
constants 𝐶𝐿 , 𝐶𝑉 as well as the packing void fraction 𝜀 and area per packed volume 𝑎 were set as given in
(Billet & Schultes, 1999).
The pressure in the scrubber was modeled to be constant, meaning no pressure drop across the packing is
considered in the internal flows.
The flash tank was modeled as equilibrium. The pressure and temperature of the flash tank were set equal
to those of the scrubber using the calculator.
The pressure of streams VU and LO was set 0.1 bar higher than the pressure of the scrubber. The
temperatures of both streams are set to the operative temperature of the scrubber.

The cooler is set to provide the stream VU with the desired temperature and the compressor with the desired
pressure.
The RB and LO streams are set to only vapor phase and liquid phase respectively to avoid flash equilibrium
with the CO2. The flow in both is specified as molar flow and the composition as a molar fraction.
To run all the simulations sensitivity analysis was used to vary the parameters for each given flow according
to Table 7.
The slip of the system is measured in the stream LXF as described in Equation 115.
The results of the simulation for the stream VU are used as a basis to model the scrubber without the flash
in the developed tool, in this case, the slip in the model ran in Aspen is measured in stream LU.
7.3 Comparison Results

The results of the comparison are divided into three: Slip, Height and molar concentration in the upgraded
biogas. To have a general picture of the results the data obtained are plotted having the results from Aspen
in the horizontal coordinate and the results from the tool in the vertical coordinate. A “perfect” match will
result in a straight line at 45°.
The deviations of each run for each parameter are averaged and presented as the general deviation with the
corresponding standard deviation. Also, the maximum and minimum deviations are reported.
7.3.1 Slip Comparison

In general, the slip calculations agree between both models. A graphical representation of the deviations is
shown in Figure 34. 21 outliers deviate significantly from the general results. These outliers, correspond to
the Scrubber model for both cases, solving for height and solving for compositions. The behavior is focalized
in the slip range between 3% and 9%, as shown on the right side of Figure 34.
These outliers correspond to all the runs where the height of the column was set to 1 m and to most of the
runs where the RB flow was set to 3 times RB nominal. This behavior is not present in the results of the Cycle
model —where the flash tank is included—. The worst deviation for those cases is -20% against -90% for the
homolog case in the Scrubber model.
The reason to have such large deviations in the Scrubber model is due to the absorption model. Since this
model is considering a high concentration of CH4 in the liquid phase outflowing from the scrubber, it might
be possible that the slip is highly at disproportion to the one due to real mass transfer. Nevertheless, the
behavior of the slip must be checked against a real operation to validate if the absorption model predicts to
a certain acceptable extend the real phenomenon.
For the results of the Cycle model, referring to Figure 35, there is a higher dispersion of the points
correspondent to the slip calculated when the model solves for the upgraded composition given a fixed
height of the column. The reason behind this dispersion is that the final upgraded concentrations are slightly
different which changes all the balances of the system including the flash tank recycled flow.

18 18 9 9
16 16
8 8
14 14
Slip calculated by Tool [%]

12 12 7 7
10 10
6 6
8 8
6 6 5 5
Cycle Model - Solve for yo4 Cycle Model - Solve for yo4
Cycle Model - Solve for H Cycle Model - Solve for H
4 4
Scrubber Model - Solve for yo4 Scrubber Model - Solve for yo4
4 4
Scrubber Model - Solved for H Scrubber Model - Solved for H
2 2 Deviation + 15%
Deviation + 15%
Deviation - 15% Deviation - 15%
0 0 3 3
-2 3 8 13 18 3 4 5 6 7 8 9
Slip calculated by Aspen Model [%] Slip calculated by Aspen Model [%]
Figure 34 General comparison results of the slip calculations. Left: Whole range. Right: Detail between 3% and 9% of
slip
For the Cycle model, another observation is that most of the blue points correspondent to the slip calculated
when the model solves for the height given an upgrading task, are under the diagonal reference line meaning
that the slip calculated by the tool reports smaller values than those calculated with the Aspen model.
Nevertheless, for the Scrubber model, the points lay in both sides of the line. Note that for higher slips, the
slip values calculated using the tool are lower than those calculated using the Aspen model.
7 7 0.5 0.5
0.45 0.45
6 6
0.4 0.4
5 5 0.35 0.35
0.3 0.3
4 4
0.25 0.25
3 3 0.2 0.2
0.15 0.15
2 Cycle Model - Solve for yo4 2
Cycle Model - Solve for H
0.1 0.1
Scrubber Model - Solve for yo4 Cycle Model - Solve for yo4
1 Scrubber Model - Solved for H 1 Cycle Model - Solve for H
0.05 0.05
Deviation + 15% Deviation + 15%
0 0 0 0
0 1 2 3 4 5 6 7 0 0.1 0.2 0.3 0.4 0.5
Figure 35 Slip deviation graphical representation. Left: All the data plotted. Right: Zoom to data up to 1% slip.
The deviations of the slip values are reported in Table 8. The average deviation is relatively low, but the
standard deviation is high. The histograms are shown in Figure 36. The outliers have a markedly impact in
the high standard deviation.

Table 8 Slip comparison results

Model Solve for Average of Deviations Standard Max Min
of the Slip deviation
Cycle Height 5.40% 4.84% 19.14% -13.11%
Upgraded
Cycle 3.57% 13.74% 40.60% -32.98
Composition
Scrubber Height -3.49% 11.73% 18.10% -90.58%
Upgraded
Scrubber -2.89% 17.70% 18.14% -164.19%
Composition
The outliers appear at the extremes of the modeled range and for high slip values. For example, the –164.19%
and one similar of –160.3% are found when the height of the column is reduced to 1 m from the nominal 4 m.
Figure 36 Histograms for Slip deviation comparison. For the scrubber model, 7 points were omitted in the histogram
since they are outliers that distort the histogram shape in the central focal area.
Referring to the histograms in Figure 36, for the Cycle model, the deviations tend to lay on the positive side
while for the scrubber they tend to lay on the negative side. These results are coherent with the observations
discussed previously.

The deviations of the tool are higher for high slip values. In the application of the tool, these are expected to
be kept in the lower range because when upgrading the methane slip should be kept as low as possible to
reduce fuel losses and avoid harmful GHG emissions.
7.3.2 Concentration Comparison

The deviations for the calculation for the upgraded composition are in general good. These deviations are
presented in Figure 37. The values are spread out around the diagonal line. For the Cycle model, there is not
a marked tendency to lie in either side. On the contrary, for the Scrubber model, there is a slight tendency to
lie in the upper side of the diagonal. This effect can also be seen in the histograms presented in Figure 38.
The histogram for the Scrubber model is skewed to the left, while the Cycle model is almost centered.
1 1
0.95 0.95
Composition calculated by Tool [mol/mol]
0.9 0.9
0.85 0.85
0.8 0.8
0.75 0.75
0.7 Cycle Model - Solve yo4 0.7

Scrubber Model - Solve yo4
0.65 Deviation + 5% 0.65
Deviation -5%
0.6 0.6
0.6 0.65 0.7 0.75 0.8 0.85 0.9 0.95 1
CH4 Composition calculated by Aspen Model [mol/mol]
Figure 37 Concentration calculation deviation graphical representation. All the data plotted.
The higher concentrations of CH4 calculated by the tool in the scrubber model belong to runs where the liquid
flow was varied, and the higher deviations were given at low liquid loads. Some cases are also given in the
low ranges when the flow of biogas is varied.
Table 9 Compositions concentrations results

Model Solve for Average of Deviations of Standard Max Min
the Concentration yo4 deviation
Upgraded
Cycle 0.21% 2.83% 4.79% -3.30%
Composition
Upgraded
Only Scrubber -1.05% 1.34% 2.86% -12.11%
Composition
The results of the deviations are presented in Table 9. Notice the low average deviation. The results are close
to zero and behave coherently between both models, the developed tool and Aspen Plus. It seems that the
Cycle model “corrects” the higher volatility of the Scrubber model, this might be due to the general mass
balance highly restricted by the pressure and temperature of the flash tank since the outflows of it are always
under equilibrium.

Figure 38 Histograms for concentration calculation deviations comparison.
7.3.3 Height of the scrubber calculation comparison

As already discussed in Subsection 3.3.4, the height of the column is a highly sensitive parameter. For small
changes in the upgraded quality, the height difference could be substantial. Due to this sensitivity, if the
saturation equilibrium concentrations are slightly different, the results of the calculations of the height of the
column can differ drastically from one model to another. This difference grows bigger the closer to saturation
the concentrations are.
7
Height calculated by Tool [m]
0
0 1 2 3 4 5 6 7 8 9
Height calculated by Aspen [m]
Figure 39 Results comparison for the calculated height of the column.
The results of the height are depicted in Figure 39. As most of the columns were calculated using 4 m as the
nominal height, there is a large concentration of results in this height. It can be observed that there is a
tendency of the tool to calculated taller columns. The Cycle model provides taller columns than the Scrubber
model.

As expected the results are spread out, note that the deviations reference lines mark +25% and –25%. This
widespread can also be seen in the histograms in Figure 40 and in the data in Table 10 where the significant
standard deviation of the results is reported. Nevertheless, the average of the deviations has an acceptable
value.
Figure 40 Histograms for the height deviations.
For the higher negative deviations, the quality of the upgraded biogas is close to the maximum equilibrium
value, is expected that for these cases high deviations may result in the calculated height. The higher positive
deviations occur in the contrary cases, where the upgraded quality is low —around 0.70—.
If the upgrading target is set following (Enefalk & Ersöz, 2016), between 78% and 83%, the height deviation
will be between ±28%, with a mean of 1.52% and a standard deviation of 16.65%. Even for this narrow range,
the results show a widespread.
Table 10 Height calculation deviations results

Model Solve for Average of Deviations Standard Max Min
of the Height deviation
Cycle Upgraded Composition -6.38% 20.40% 31.80% -64.93%
Only Scrubber Upgraded Composition 1.52% 20.54% 46.66% -54.02%
Even if the general behavior of the height calculation gives acceptable results, it is important to point out
that this is just a coherence comparison between two models that have not been tested against real
operations. It is not possible to conclude if any of them is predicting the given conditions accurately. Thus
the results should be interpreted with caution.

8 Sensitivity Analysis
As it has been described the tool performs two different core calculations. First, it solves for the slip of the
system and all mass balances —Cycle model—, second, it calculates the dimensions of the scrubber —
Scrubber model—. The sensitivity analysis is divided in two, one for each of these calculations.
For the cycle-loop calculations, where slip and mass balance are calculated, the most influential parameters
are the absorption model and the applicability of Henry’s law in the range of operation of the tool. The former
is the one that introduces the higher uncertainties to the model since it is an assumption not verified
experimentally rather than a deduced description of the behavior of the phenomenon of mass transfer of
CH4 in a biogas scrubbing column.
For the scrubber height model, there a set of parameters that influence in a higher or lower degree the
calculations. For example, the exponents of the dimensionless numbers that are introduced in the vapor
volumetric mass transfer coefficient have a direct influence on the HTU values. According to (Billet & Schultes,
1999) the values of those exponents fit the behavior in absorption columns. Nevertheless, the values are the
result of extensive experimentation and fitted to a large variety of cases. By modifying these parameters, the
results might change, the question that arises is which are the exponents that fit better the description of a
biogas upgrading column? The purpose of the sensitivity analysis is to evaluate the influence of those
exponents in the general results of the height calculations.
Another set of parameters that affect the scrubber model are the packing constants. According to (Billet &
Schultes, 1999), these are the product of extensive testing. If a new packing material is developed, a new set
of tests should be implemented to define the constants. By comparing the calculated height of an upgrading
column using three geometrically similar packings of the same material and size, the influence of these
packing constants was analyzed.
8.1 Sensitivity Analysis for the Cycle-Loop Model

The CH4 absorption phenomena model is presented in Subsection 4.2. The two extreme alternatives were
tested to analyze the sensitivity of the modeling tool to the CH4 absorption model implemented: the
equilibrium model and the flash equilibrium discussed in the mentioned subsection.
The following abbreviations are used to designate the CH4 absorption models:
EQ Equilibrium model. Equation 123.
FE Flash equilibrium model. Equation 124.
CM Combined model. Equation 125.
Results of Implementing EQ and FE Models
The same runs are calculated using these two alternative models and compared to the used one. The results
variations are shown in Table 11 where the summary of the deviations is compiled. The summary is also
presented graphically in Figure 41 and Figure 42.
Height Analysis Variations:
• Scrubber model: neither the average values nor the standard deviations change considerably while
using different CH4 absorption models.

• Cycle model: The EQ model tends to calculate lower columns, while the FE higher ones. This result is
expected since for the FE model, to achieve a similar slip value the recycled vapor flow increases.
Table 11 Sensitivity analysis results summary. The method the tool uses is CM —blue text—.
Average Standard Deviation
EQ CM FE EQ CM FE
Height 1.22% 1.52% 1.80% 20.71% 20.53% 20.34%
Scrubber -
Concentration yo4 -1.02% -1.05% -1.09% 2.83% 2.83% 2.85%

Only
Slip – solved H 13.41% -4.06% -21.28% 15.30% 17.92% 22.03%

Slip – Solved yo4 13.41% -3.49% -19.99% 15.30% 17.67% 21.97%
Height 3.41% -1.73% -6.38% 18.60% 19.42% 20.40%
Scrubber +
Flash Tank
Concentration yo4 -0.36% -0.07% 0.21% 1.31% 1.31% 1.34%

Slip – solved H 5.41% 5.41% 5.40% 4.84% 4.84% 4.84%
Slip – Solved yo4 10.33% 6.86% 3.57% 13.41% 13.26% 13.74%
Average - Scrubber Only Standard Deviation - Scrubber Only

25% 25%
EQ: Equilibrium
20% 20%
CM: Combined
15% 15%
FE: Flash Equilibrium
10% 10%
5% 5%
0% 0%
H yo4 Slip - Solve Slip - Solve H yo4 Slip - Solve Slip - Solve
-5% -5%
for H for yo4 for H for yo4
-10% -10%
-15% -15%
-20% -20%
-25% -25%
Figure 41 Average and Standard deviations for the calculations considering only the scrubber -No flash tank-
Average - Scrubber + Flash Standard Deviation - Scrubber + Flash

25% 25%
EQ: Equilibrium
20% 20%
CM: Combined
15% 15%
FE: Flash Equilibrium
10% 10%
5% 5%
0% 0%
H yo4 Slip - Solve Slip - Solve H yo4 Slip - Solve Slip - Solve
-5% for H for yo4 for H for yo4 -5%
-10% -10%
Figure 42 Average and Standard deviations for the calculations considering scrubber and flash tank.

Concentration Variations:
• Scrubber-only and Scrubber + Flash tank: neither the average values nor the standard deviations
change considerably while using different CH4 absorption models.
Slip Variations:
• Scrubber-only: The slip difference varies drastically between models. For the EQ model, the slips are
lower than the reference ones (Aspen model), while for the FE the are higher. The standard
deviations are higher for the FE and lower for the EQ compared to those of the CM. An important
remark is that this slip will have a strong influence on the recycled flow from the flash tank when
present. This influence can be seen in Figure 43.
• Scrubber-only and Scrubber + Flash tank: As expected the slip when solving for height is the same
regardless of the absorption model since the slip depends on the equilibrium at the flash tank which
depends on Henry’s law. The recycled flow, as explained in the previous bullet point, would have a
considerable variation. The consequence of this condition is that the heights vary to compensate for
the absorption model used. That is why the heights for the EQ model are shorter than those
calculated with the FE model.
If solving for concentration, given the height of the scrubber, the difference is also marked, the cause
of it is the recycled CH4 flow. For high recirculation, proper of the FE model, the amount of CH4
transferred to the liquid is higher which results in a higher CH4 molar fraction in the recycled flow
𝑦𝑓4 , which results in a higher slip because of Equation 115 (repeated here for convenience) and the
fact that 𝑋𝑓4 = 𝑦𝑓4 ⁄𝑚𝑦𝑥𝑓4 . This can be seen in the right side of Figure 44 where the slip from the FE
model tends to lie over the diagonal.
𝐿 ∙ 𝑋𝑓4 𝑠𝑙𝑖𝑝
= = 𝑠𝑓 (115)
𝑅𝐵4 𝑅𝐵4
All standard deviations are very similar between the models.
18 18
16 16
14 14
12 12
10 10
8 8
6 6
4 Scrubber FE - Solve for yo4 4

Scrubber CM - Solve for yo4
Scrubber EQ - Solved for yo4
2 2
Deviation + 15%
Deviation - 15%
0 0
0 2 4 6 8 10 12 14 16 18
Slip calculated by Aspen Model [%]
Figure 43 Sensitivity analysis. Calculated slip solving for yo4 on the Scrubber model. FE, CM and EQ absorption models.

7.0000 7
Cycle FE - Solve for yo4 0.4750 Cycle FE - Solve for yo4 0.475
Cycle EQ - Solve for yo4
Cycle EQ - Solve for yo4 Cycle CM - solve for yo4
6.0000 Cycle CM - solve for yo4 6 0.4250 Deviation + 15% 0.425
Deviation - 15%
Deviation + 15%
Deviation - 15% 0.3750 0.375
5.0000 5

0.3250 0.325
4.0000 4
0.2750 0.275
3.0000 3 0.2250 0.225
0.1750 0.175
2.0000 2
0.1250 0.125
1.0000 1
0.0750 0.075
0.0000 0 0.0250 0.025

0 1 2 3 4 5 6 7 0.025 0.125 0.225 0.325 0.425
Figure 44 Sensitivity analysis. Calculated slip solving for yo4 on the Cycle model (Scrubber + Flash). FE, CM and EQ
absorption models. Left: All the data plotted. Right: Slip Detail from 0.025 to 0.5%.
8.2 Scrubber Model Sensitivity Analysis

The development of an in-depth sensitivity analysis of the model that calculates the height of the scrubber
escapes the scope of the present study. The number of possible variations and their interrelation is too high
to be treated at this stage of the tool development, especially before comparing the model to real scrubbing
performance. There are approximately 25 different parameters that the authors of the method (Billet &
Schultes, 1999) introduce to account for different phenomena.
Among all the parameters, there are six packing constants that are introduced in different calculations to
account for the influence of the packing in the model. For example, the Cs and CFl constants are used to
calculate the resistance to flow coefficient, or the CL and CV are used to calculate the volumetric mass transfer
coefficients. There are also two exponents of dimensionless numbers that modify the volumetric mass vapor
coefficient. The following analysis aims at uncovering the behavior of the results by varying these to sets of
named parameters.
8.2.1 Dimensionless Exponent Changes in the Volumetric Mass Transfer Coefficient

Referring to Equation 82, repeated here for convenience, the exponents 3/4 and 1/3 where formerly 1/2 in
the derivation of the equation. The change of these is justified by (Billet, 1995) because the changed values
adjust the coefficient to the real mass transfer of the vapor phase.
3 𝟏
𝟑
𝑢𝑉 1 𝑑ℎ2 1 𝑎 ∙ 𝜂𝑉 𝟒 𝜌𝑉 ∙ 𝐷𝑉 𝟑 1
𝐻𝑇𝑈𝑉 = = ∙ 3 ∙ 𝑢𝑉 ∙ (𝜀 − ℎ𝑙)2 ∙ 𝐷𝑉 ∙ ( ) ∙( ) ∙ 𝑎 (82167)
𝑎𝑝ℎ ∙ 𝛽𝑉 𝐶𝑉 2 𝑢𝑉 ∙ 𝜌𝑉 𝜂𝑉 𝑝ℎ
( 𝑎 )
𝑎
To test the sensitivity of the model to these two exponents a series runs were made by using 1/2 for both.
• One set changing only 3/4 to 1/2.

• One set changing only 1/3 to 1/2.

• One set changing both to 1/2.
The results are compared to those obtained from the tool using the Billet assigned exponents.
Results of The Change in Exponent s
Figure 45 shows the results of the comparison. The 1/3 exponent, when changed to 1/2, produces shorter
scrubbers while when the 3/4 exponent is changed to 1/2, the scrubbers are taller. An interesting observation
is that when both are changed the heights of the scrubbers resulted even greater than the ones from
changing only the 3/4 exponent.
10 10 6 6
Height calculated with the Tool and (1/2) exponents
Height calculated with the Tool and changed

9 9
5.5 5.5
8 8
7 7 5 5
6 6 exponents [m]
4.5 4.5
[m]
5 5
4 4
4 4
3 3 Both exp. Changed
Both exp. Changed
3/4 to 1/2 changed 3/4 to 1/2 changed
2 2 3.5 3.5
1/3 to 1/2 changed 1/3 to 1/2 changed
1 Deviation + 25% 1 Deviation + 25%
0 0 3 3
0 1 2 3 4 5 6 7 8 9 10 3 4 5 6
Height calculated with the Tool and (3/4) and (1/3) Height calculated with the Tool and (3/4) and (1/3)
exponents [m] exponents [m]
Figure 45 Height comparison between the results obtained using tool with the original Billet exponents of 3/4 and
1/2 and those obtained with the tool using 1/2 exponent.
When both exponents were changed, the height of the columns increased around 10% on average. It can be
concluded that the variation of these exponents does not change the results drastically. The model seems to
have a low sensitivity to changes in these exponents.
8.2.2 Packing Constants Change

There are in total six packing constants that adjust the fluid dynamic theoretical equations to the behavior of
the different packings. This analysis aims at checking how sensitive is the model to changes in the set of
constants. The primary thought behind this is to test if it is possible to assign the values of the constants to
newly developed packing by using known similar packing constants. For example, if a 50 mm packing material
was developed, can the constants of other 50 mm packing material be used as a starting modeling point?
To test this influence, a set of runs different packings were compared to the results obtained using 50 mm
plastic pall ring as a reference. The packings used were all 50 mm plastic:
• Ralu rings • Hiflow ring

• Ralu Flow • Hackette
• NOR PAC

Results of The Change in Packing Constants
The results are presented in Figure 46. The average deviation is plotted in dotted lines, and the respective
values can be found in the labels on the figure. As a reference of the packings, a picture of each is presented
in Figure 47. The highest deviation was 25% which is given by the NOR PAC and Hiflow rings. Surprisingly
Hackette ring that has such different shape and it is 5 mm smaller in diameter gives deviations of 17%. Ralu
ring and Ralu flow packings show a lower deviation, being Ralu flow the closest to the reference values with
6.4% deviation.
8 8 4.5 4.5
4.3 4.3
Height calculated with different packings [m]

Height calculated with different packings [m]
7 7
4.1 4.1
6 6
3.9 3.9
Ralu Flow:
5 5 Av.Dev 6.4%
3.7 3.7
Ralu ring:
Av.Dev -10.2%
4 4 3.5 3.5
Hiflow-ring:
Av.Dev 25.5%
3.3 3.3
3 3 NOR PAC ring:
3.1 3.1 Av.Dev 26.3%
Ralu Flow: Av.Dev 6.4% Hackette:
2 2
Ralu ring: Av.Dev -10.2% 2.9 2.9 Av.Dev -17.8%
Hiflow-ring: Av.Dev 25.5%
1 NOR PAC ring: Av.Dev 26.3% 1 2.7 2.7
Hackette: Av.Dev -17.8%
0 0 2.5 2.5
0 1 2 3 4 5 6 7 8 2.5 2.7 2.9 3.1 3.3 3.5 3.7 3.9 4.1 4.3 4.5
Height calculated with the Pall Ring packing [m] Height calculated with the Pall Ring packing [m]
Figure 46. Height comparison between the results obtained using tool with Pall ring and those obtained with the tool
using Ralu Flow, Ralu Ring, Hiflow ring, and NOR PAC ring, packing materials.
Even if the packing materials look similar, the results can vary by 25% like in the case of Hiflow® Ring and
NOR PAC Rings. It may be concluded that packing with the similar size and similar shape will behave similarly
with an expected deviation up to 25%. The use of improper constants introduce large uncertainty in the
process and must be treated cautiously.
Figure 47 Packing materials compared. Left to Right: Pall Ring, Hiflow ring, NOR PAC, Ralu Flow, Ralu ring, Hackette.
Source (Raschig Gmbh, 2018) except for Hiflow Ring which was obtained from (RVT Process Equipment GmbH, s.f.)

9 Discussion
The tool developed has two different models embedded, one for the mass balance and one that solves for
the dimensions of the scrubber. Both models have their limitations and should be used with caution.
The mass balance model is developed around the three compounds that interact, H2O, CO2, and CH4. The
water acts only as a transporter of dissolved gases and the evaporation in the system is neglected. Thus the
influence of the vapor phase of water is neglected.
Some remarks are relevant to state; the raw biogas is assumed to be saturated with water vapor since in the
digester the sludge is a water solution, and the biogas is formed inside this aqueous media. Once the raw
biogas is cooled down to the upgrading temperature, some of the liquid will condense, but at the exit, it will
remain at saturation conditions at the lower temperature. The water vapor pressure is solely dependent on
temperature (Nock, et al., 2014), and since temperature in the scrubber is practically constant all over the
packing material, there is no mass transfer from the vapor phase and the liquid phase of water, meaning that
there is no change in the phase water flows in and out of the scrubber.
If water is neglected in the vapor phase, the partial pressures of CH4 and CO2 will be slightly higher than
those calculated considering the water vapor phase presence. The difference of the partial pressure can be
seen using an example as follows. For a temperature of 15°C the water vapor pressure is calculated according
to Buck equation (Vömel, 2011):
𝑇
(18.678− )∙𝑇
234.5 (168)
𝑊𝑣𝑝 = 0.61121 ∙ 𝑒 257.14+𝑇 ∙ 1000 = 1705 𝑃𝑎 = 0.01705 𝑏𝑎𝑟
Where 𝑊𝑣𝑝 is the water vapor pressure in Pascal, and 𝑇 is the temperature in °C.
If a dry mixture of 55% CH4 and 45% CO2 at 10 bar is used as a reference, the partial pressure of each would
be: 5.500 bar and 4.500 bar respectively. If the same mixture were at saturated conditions, then the partial
pressure would be reduced to 5.490 and 4.492 bar. The difference is only –0.17%
For a case with low pressure, for example of 2 bar, with a mixture of 95% CH4 and 5% CO2 the dry partial
pressures would result in 1.9 and 0.1 bar respectively. In saturated condition, the partial pressures would be
1.883 and 0.099 bar. The difference is only –0.85%. In the present study, this error is considered too small.
Nevertheless, according to Henry’s law, the solubility in water is directly proportional to the partial pressure
of the vapor phase. If a higher partial pressure is used, then the mass transfer into the liquid phase would
result increased in the same proportion as the partial pressure. In other words, for the 2 bar example, the
mass transfer calculations would be higher by 0.85% than if considered in a saturated mixture.
The influence of the calculated higher compositions in the outflowing liquid from the scrubber has an impact
on the flash equilibrium results. The flash tank itself would have saturated recirculation mixture, and the
composition would change in the same manner as in the scrubber. For the current stage of the tool
development, it is considered not necessary to address the introduction of the water as a component of the
vapor phase.
If the tool is further developed, it should be evaluated if introducing the complexity inherent to including the
water as vapor component is worth the investment, since the deviations as shown are in the order of 1%.
The mass balance for the CH4 component uses an absorption model that is not connected to the fluid
dynamics model, nor to mass transfer coefficients, like the Higbie one used for CO2. As it was shown in the
comparison against Aspen plus, there is a strong influence of this absorption model in the whole system.

There are some alternatives other than considering the absorption as treated in Subsection 4.2. One
possibility is to model the mass transfer of CH4 in the same fashion as CO2 by using the penetration model.
If a penetration model is implemented for CH4, then the mass balance cycle must be integrated into the
scrubber cycle to solve both mass balance equations at the same time. This strategy requires a more complex
implementation where for each iteration for the mass balance the scrubber must be solved as well. Before
implementing a more complex model, it should be analyzed if the improved accuracy is worth the extra work.
For the CO2 mass balance, the model associates a CH4 flow to a correspondent CO2 flow. This dependency
determines the inlet and outlet concentrations of the scrubber and assumes that the scrubber is capable of
achieving the separation. If the tool will solve for height, then is only a matter of solving the scrubber model.
However, if the tool is solving for outlet concentrations, then the calculation process is iterative until the
calculated height is equal to the given height.
This height iteration consumes a considerable amount of resources and can take up to 40 seconds to solve.
If another solving strategy for the mass balance is implemented this time might be reduced. It is worth
investigating the alternatives to solve the cycle and the scrubber in the same process.
The Billet methodology implemented for the scrubber is for mass transfer between two phases flowing in a
counter-current fashion. Such processes can be distillation, rectification, absorption, or desorption. The
model proposed by Billet is a general tool, and, in the development, large amounts of tests were performed
to adjust the theoretical equations to the real flow and mass transfer behavior on packed columns. These
adjustment points reflect the average of all studied cases and are not specific for biogas scrubbers.
The influence of the fluid properties in the model might have a small impact versus the simplifications and
assumption of the model itself. To minimize the negative influence of the calculation of the properties high
detail models were implemented in the tool as the one for the vapor density where the Peng Robinson
equation with mixing rules using fitted data was implemented, or for the diffusivity where recent correlations
for CH4 and CO2 in water were used as described in Subsection 3.4.
Most of the correlations, except for the vapor viscosity, are all binary based, meaning that the influence of a
third component is not considered in the interaction. This simplification might have a particular neglected
influence in the absorption of CH4 and CO2 in the water since for the slope of the equilibrium curve the Henry
constant of the binary equilibrium is used, and the presence of the third species is neglected.
Following the methodology development described in detail by the author in his work (Billet, 1995), there
are several limitations and restriction to where the model is valid and tested. Indeed, Biogas upgrading is not
tested. The densities for the vapor phase in high-pressure scrubbing are several times higher than those of
the tested systems. The same occurs with the molar ratio between the vapor and the liquid phases; the biogas
values are out of range of the tested systems. It is necessary to test the validity of the model against the real
operation of biogas upgrading systems.
An important parameter that is introduced by Billet in the methodology is the interfacial area which is
calculated using dimensionless numbers, and the exponents are adjusted according to testing. The values
obtained in the tool, for specific cases are several times higher than those referenced in the authors work. If
testing using biogas systems is implemented the exponents for these values can be correctly adjusted.
In biogas upgrading the flow parameter Ψ, is much greater than 0.4, in some cases is one order of magnitude
higher, meaning that the inversion point was surpassed and that the vapor flows in bubbles. The original
theoretical foundation of the model is for mixed flows, where the vapor phase is the continuous phase, and
the liquid is the disperse phase. The methodology is clear about the inversion point and of the changes it
introduces to the model. For example, some constants are changed if the flow parameter is greater than 0.4.

Nevertheless, there is no direct stated limitation on the value for the flow parameter. Is uncertain if the
model will hold for such large flow parameter values as those found in biogas upgrading.
Since the gas is the disperse flow, it is not entirely clear if the calculation of the interfacial area holds or it is
limited to some extent to the flow parameter. It should be pointed out that the interfacial area has a
profound influence on the HTU calculation. Miss calculating the area would result in a significant error.
The Billet model modifies the packing constants 𝐶𝑆 and 𝐶𝐹𝑙 depending on if the flow has surpased the
inversion point or not. Notice that these constants are crucial in the calculation of the resistance to flow
parameter 𝜉. This modification might be enough to make the model consistent to any high flow parameter
value. It should be noticed that this resistance to flow is the parameter that accounts for the presence of the
packing material in the flows. It is similar to the resistance to flow caused by the internal rugosity of the wall
of a pipe when calculating pressure drop in a piped system.
The model has several adjustment points where is tweaked to predict in a general way any counterflow
scrubber. This broad spectrum of possible applications might give the impression that the results have
intrinsically very high uncertainty and inherited errors from the extensive formulation itself. Nevertheless,
according to (Billet & Schultes, 1999) the error of the validation of the model is only 5% for the loading and
flooding point, 6.7% for the column holdup, and 12.4% for the mass transfer efficiency.
These excellent results of the validation of the model done by the authors confer a high degree of trust in its
implementation. At the same time, the open possibility to adjust the model bring even higher positiveness
to develop it further and reach accurate and reliable results specifically for biogas upgrading. All of this
translates into the need to run experimental tests to continue on the development path. These tests can be
performed driven by the economic interest of developing small-scale upgrading systems by IMBAB.
Another advantage of the tool is the possibility to change the absorbent media. The tool can easily be adapted
to other liquids, most of the functions that calculate the properties of the fluids can be extended to other
substances. For example, the slope of the equilibrium curve 𝑚𝑦𝑥 can be easily calculated for other substances
by knowing the Henry constant parameters. The density, viscosity and surface tension can be coded as well,
and the model can run without making further or more complex modifications.
One of the characteristics of the model is the use of six constants assigned to each packing material. This
issue could be a benefit and a drawback at the same time. A benefit because it allows high accuracy and
detail in the model and a drawback since it is necessary to find by experimentation these constants, which
requires resource investment. It should be financially evaluated if developing the constants for new packing
material beneficial or not. This evaluation depends of course on expected sales volume and variability of the
system, meaning if the units that would be developed have a wide range of operation where accurate
prediction of the behavior would contribute to the success of the business.
For the time being, the tool developed should be used with caution when solving for the height of the column.
The uncertainties of the model have not been evaluated nor analyzed, and the result might have a significant
offset against the real values.
The results for the mass balance, flows, and slip can act as a guiding tool and are prone to have some
uncertainties especially if a flash tank is used since it acts as the bottleneck. The flash tank might operate far
from equilibrium, or it could operate with phase entrainment, which would change the results drastically.
Regardless of the uncertainties and testing needed, the tool can still be used as a guiding tool to obtain
preliminary data or to run first-time estimations. The comparison process shows that even if the results are
not reliable, they are coherent meaning that they hold proportionality when varying operating parameters.

The energy and power analysis module can be tweaked and adjusted if the equipment is known. For example,
the isentropic efficiency values, the compression ratios, the mechanical efficiencies can all be adjusted to the
exact values of the real machinery installed.
The pressure drop of the system has not been calculated; the values used are only a percentage of the
operating parameters. It must be pointed out that if the column operates too close to the flooding point the
pressure drop across the column becomes considerably high and the overpressure considered in the tool
might not be sufficient to overcome such pressure drop.
The tool can be updated to include the pressure drop through other installed elements such as valves, filters
and other accessory equipment, as well as piping, tees, elbows and similar accessories.
Using the energy and power analysis of the tool, the user can run partial loads analysis and can validate the
benefit of a change of operating parameters. For example, if the decrease in flash pressure to reduce the slip
is worth the extra energy needed to recycle a more massive vapor flow from the flash tank. Another example
is if it is worth to reduce the operating temperature to increase the upgrading quality of a scrubber by
increasing the energy needed to cool both inlet flows, the biogas and the water. It also shows the side effects
of a change in the operating parameters, for example by reducing the temperature to achieve higher quality
in the upgraded biogas, the slip increases, so the designer might opt to reduce the flash pressure to
compensate for the additional slip.
If testing is performed and the model is appropriately adjusted the tool would provide fast reliable, accurate
and useful information to the designer of the upgrading system.

10 Sustainability Analysis
Raw biogas can be used to generate electricity and heat as well as for cooking. Nevertheless, it is not a
suitable choice for transportation fuel. Therefore, the need to upgrade to qualities around 82% (Enefalk &
Ersöz, 2016). If an upgrading system is implemented in a biogas unit, it would be able to act as a core source
to satisfy most of the energy demands.
Dispersed population areas, small agricultural sites, isolated communities, among others would access locally
produced renewable energy if a biogas system were implemented. The development of a small-scale
upgrading unit aims at widening the applicability of the use of raw biogas to include the supply of fuel
transportation.
Another significant benefit of implementing an upgrading unit is that it would make possible the energy
storage by using compressed upgraded biogas in high-pressure cylinders. This feature complements the
intermittency of other renewable sources like wind, hydropower, and solar, making the biogas unit the
needed flexible link of the system, allowing decarbonization of the energy system.
To have a better understanding of the sustainability of an upgrading unit, the analysis is broken into the three
fundamental pillars: Economic, Environmental, and Social.
Economic Sustainability
As it was described in the background section, industrial upgrading has had an outstanding development in
the past years. The variety of upgrading systems available nowadays is considerable, and efforts have been
invested towards small-scale operations.
To implement an upgrading system that can compete with other energy sources is the key to success. This
analysis assumes that the system will be installed in small agricultural sites, like family farms, or far disperse
communities like small villages where the raw biogas production is between 10 Nm3/h and 100 Nm3/h.
The access to energy sources of these type of populations is usually restricted and expensive. Their needs are
commonly supplied via fossil fuel or by burning biomass for heating and cooking. Biogas systems that operate
in these locations should be standalone units, reliable and the operation and maintenance should not rely
on the supply of unique consumables, frequent replacement of parts, or specialized technical service. Water
upgrading complies with these criteria.
The present study did not investigate on the economics of upgrading, but a qualitative analysis can be
performed to have an insight if high-pressure water upgrading can be an economically feasible technology
to implement in the locations in question.
The typical equipment that composes an upgrading unit is a compressor, condensing filter, H2S removal unit
—if the concentration in raw biogas is high enough—, biogas cooler, scrubber, optional flash tank, stripper,
water pump, water cooler, water filter, and pressure regulators for biogas and water. All these parts are
common to the industry, and their development stage can be considered as mature. The only unit that would
have to be further developed is the water scrubber. Although scrubbing is a highly known process widely
implemented in the petrochemical industry, there is still room for development for small-scale biogas
upgrading systems.
The scrubber materials, production techniques, and designs are highly dependent on operating pressure and
volume. Some characteristics make biogas high pressure scrubbing costly. Among the most influential are:
The biogas is corrosive and combustible, the operating pressures can produce relatively high stresses in the
column requiring thick walls, and it consumes large amount of water, even if a stripper is used.

Designing innovative scrubbers could be the solution to these challenges and may provide competitive prices
that would make possible the implementation of the small-scale units. Recently a price breakdown has
happened for control elements, regulators, instrumentation, specialized materials, and production and
manufacturing techniques. Combining all these elements is expected that the production price for upgrading
systems should decrease as well.
From the perspective of the user, the cost of the biomass fed into the system is low, since in most cases
would be waste material, like manure or agricultural discard material. In some cases, the user could grow
energy crops as a marginal operation in portions of land where their primary activity is not feasible. For
example, a small farm can have seasonal lakes due to rain seasons, where algae can be cultivated and
harvested as an energy crop.
Another benefit of using a biogas unit is the digestate that results from the anaerobic digestion. This material
serves as an excellent fertilizer and helps to close the material loop, leading the site towards a circular
economy. The use of locally produced fertilizer reduces the expenses and operation of the site what increases
the feasibility of the biogas unit as a system.
The potential of using upgraded biogas as CBG is an important feature that tackles the problematic link
between fossil fuels and transportation. The solution proves even better for isolated sites as the ones focus
of this analysis. Fossil fuel prices tend to be higher and quality lower the further the site is from central areas.
Drying the upgraded biogas and compressing it to around 200 bar is required to provide CBG. The technology
to do these tasks is proven and has spread to many countries that have CNG stations. There is no technical
limitation to implement a compressing unit in a biogas system. One of the additional advantages is to use the
high pressure to store excess production of biogas in cylinders. Storing biogas frees the production from the
consumption allowing flexibility and independence from each other.
Since the refueling station is located close to the vehicles resting place, there is room for optimization. The
autonomy of the vehicle is directly related to the size of the storage cylinder and pressure. The higher the
pressure, the greater power and energy is needed to compress. By optimizing the amount of fuel needed in
a driving cycle the amount of energy consumed to compress is also optimized.
A factor that must be clarified is that the CNG sector might be highly regulated in some countries and that
the private application of the technology might be forbidden. This restriction is an issue that should be
treated case dependent but plays a vital role in the potential of implementing this solution in the
mentioned sites.
Environmental Sustainability
The analysis of the environmental sustainability of biogas upgrading can be divided into two perspectives.
The first is what is the impact of upgrading, versus not upgrading. The second perspective is inquiring if
upgrading is energy beneficial from a renewable system perspective. The general assumption for this analysis
is that a digester is in place and that the biogas is produced.
Impact of upgrading versus not upgrading
As described in Subsection 1.1, raw biogas can be used as an energy source for cooking, heating and power
generation. A chief factor is that cleaning should be performed to preserve the life expectancy of the
equipment burning the raw biogas. Upgrading is a process that opens new alternatives to the use of biogas.
Some of the most important are the use as transportation fuel, its injection into natural gas networks, and
its storage where production can be unlinked from consumption.

The consequences of upgrading are CH4 emissions from slip if there is no waste gases treatment, the use of
energy to upgrade, the possible contamination of water sources or air pollution. If no pre-cleaning of the raw
biogas is performed during the upgrading process, the contaminants will be transferred to the water. Once
the loaded water passes through the stripper CO2, CH4, and some of the contaminants will be regenerated in
the air. The impact of CO2 can be considered neutral, the impact of CH4 can be analyzed by comparing the
emissions avoided by the use of the upgraded biogas versus the use of the traditional fuel. The impact of the
contaminants like H2S, NH3 or VOC, must be analyzed as a separate problem, since its origin is not the
upgrading process, and its final disposal depends on the cleaning process of the raw biogas or the treatment
of waste gases. For example, one of the most popular ways of treating H2S is by chemical reaction with Iron
to form FeS salts, which neutralizes it and avoid the emission of the corrosive compound.
A fact that should be pointed out is that the use of mechanical equipment in the upgrading process possess
potential harm to the environment since compressors, pumps, and refrigeration units are commonly oil
lubricated. Especially for piston oil-lubricated compressors, the oil gets in contact with the compressed fluid,
and by this, it leaks out into the flow. This phenomenon is particularly crucial if the oil is transferred into the
water flow since this contamination has a remarkable impact if the water is disposed of without treatment.
A life cycle analysis could provide answers to questions like if the use of an upgrading unit does bring benefits
in the overall run. The construction and operation of the unit carry intrinsic emissions. For example, for plastic
packing material, the life cycle is several times shorter than the life cycle of the scrubber as a unit (Sundberg,
2018). Even if other packing materials are used like metal or ceramics, there still is the need to perform
maintenance like washing and sterilization since bacteria are prone to grow on the packing surface.
In case of malfunctioning, some risks must be considered as direct CH4 emissions, water contamination with
oil, low pH levels resulting of high levels of CO2 dissolved, or biological contamination product of the bacteria
growth in the scrubber, which gets transferred to the water.
Energy Analysis Cycle of an Upgrading Process
Two uses can be considered to analyze the influence of upgrading from the renewable energy perspective,
one is as a transportation fuel, and the other is as stored energy.
As a transportation fuel, the analysis lies on the avoided fossil fuel used, especially in remote locations, where
the impact is even more profound due to higher transport needed to place the fuel in these places, and higher
losses and pollution due to leaks during the handling process. Biogas has the potential of replacing 100% of
fossil fuels for farms and isolated small populations. There are several commercial mature technologies to
convert petrol internal combustion engines to use biogas as fuel. These technologies have been developed
thanks to the recent boom of the natural gas industry.
Assuming correct treatment of waste material from upgrading, like H2S and slipped CH4, the emissions from
burning biogas may be considered carbon neutral, which make the replacement of the fossil fuels close to
complete success. Nevertheless, some limitations are present. The conversion of diesel engines is costly and,
in many cases, not cost beneficial. Small manual petrol driven tools, like mowers, chainsaws, and others, even
if possible to convert to biogas, have practical issues. Some of these issues are the weight of the storage
cylinder and the cost of the conversion which might make the fuel replacement too tricky to achieve.
In these cases, the transition to biogas could be achieved when renewing the equipment once the lifespan
has been depleted. For small equipment there is a market potential to be developed and if biogas becomes
one of the driving forces for agricultural development the offer of this equipment may be rapidly fulfilled.
The conversion of diesel equipment is far more expensive and complicated than for petrol units. The
challenge is that CH4 does not work correctly in a diesel cycle. If a conversion is to be performed, spark plugs

should be introduced in the engine which is a costly and complex task. An option is to replace the diesel units
with CBG units once their life cycle has ended. Nevertheless, for heavy machinery, it seems to be a lack of
options. As an example, Valtra, a Finish tractor manufacturer that is one of the few that offers a biogas model,
has a unit that runs on a mix of CBG and Diesel with a ratio of 83% and 17% respectively. In Figure 48 a picture
of the tractor is shown.
Figure 48 Valtra Diesel - Biogas tractor. (Valtra, 2018)
For the case of agricultural Diesel machinery, it could be possible that the lack of offer of biogas —or even
natural gas— competitors is motivated by the lack of the availability of the fuel in the targeted market.
Refueling stations are not commonly located in rural areas. This situation is a classic chicken-and-egg
situation. Small-scale upgrading units might provide the leap to break the causality dilemma.
Biogas can be easily stored using high-pressure cylinders of even by cooling it down to its liquid state as LBG.
As a source for power generation, it may complement perfectly unpredictable and intermittent sources like
solar and wind. One of the advantages is that the power ranges to generate are broad, from few kilowatts
using internal combustion engines to several Megawatts using turbine engines.
For a small farm or an isolated small village, a combined system could prove to be grid and fossil free by
implementing different renewable technologies and using biogas as the core balancing link. This possibility
implies that upgrading must be implemented. There are a set of options in how locally produced biogas can
be integrated into energy systems; the options are increased if upgrading is introduced. It should be clarified
that the upgrading does not imply processing the totality of the raw biogas. Some of it might be more
beneficial to be directly used as in the case of cooking or heating with a simple cleaning process.
Social Sustainability
A key social development factor is access to energy. For isolated population or small farms, this access is
often restricted or costly. Implementing a biogas system with an upgrading unit might help the development
of these locations with a low impact as already discussed. Socially, some considerations might be useful to
analyze before introducing such systems in specific regions.

The use of biogas can boost the development of a site since it could provide low-cost energy for typically
expensive applications like transportation. Marketing farming products usually imply the transport of the
goods to consumption places. Lowering the cost of the transport expense and lowering the cost of farming
by reducing the cost of fuel can help the farmer achieve a better life quality. In some cases, the use of biogas
might introduce renewable electricity to grid disconnected locations which widens the developing options.
The implementation of biogas systems has, as any other option, an investment cost. In many cases, the access
to new technologies is pushed by subsidies either financed by governmental programs, or by nonprofit
organizations. It must be carefully studied when a program is being developed, that there is fair access for all
of the stakeholders to avoid local rivalries within those how can access the system and those who do not.
Since the upgrading of the present study uses water as the absorber, it should be pointed out that there is
an intricate connection between energy and water, and that in some occasions competition might rise for
the water resource.
If several neighboring farms or villages share the water source, the implementation of an upgrading unit
should be carefully controlled since the contamination of water might bring disputes among the users. For
example, the release of carbonated water into a river can have a negative influence on biodiversity since the
pH levels can be changed and therefore the local ecosystem can be affected.

11 Conclusions and Further Work
11.1 Conclusions
• The tool developed solves two systems which are intricately dependent, the mass balance of the
upgrading unit and the operation of the scrubber. Errors or uncertainties in one of the systems will
reflect on the results of both models.
• The scrubber model limits were exceeded, and the high-pressure water scrubbing process is not
covered in the tests developed by (Billet, 1995).
• The tool must be tested against real operations.
• The results are promising since there is a multiplicity of adjustment points in the model, and its
operation is stable and coherent.
• The methane absorption model should be evaluated and analyzed using a more in-depth approach.
It must be decided if a complex model like the penetration model should be implemented or a
simplified one similar to the one used in the current tool holds accurately enough.
• The tool might help IMBAB in the development of upgrading units by providing preliminary results;
it may also be a ground base to build a more robust tool once testing and validation are done.
• The tool can be adapted to use other different absorbent media.
• The use of high-pressure water scrubbing can be implemented in small-scale if economically viable
to provide access to renewable energy to isolated populations and small farms. The challenge is to
find low-cost solutions for the system, since the other challenges, i.e., environmental issues can be
overcome by implementing feasible known solutions.
• The use of a flash tank can achieve up to 0.25% slip or lower values, but the increase in the energy
needed to process the recycled flow must be considered as a side effect. There is a trade-off between
the slip and the energy associated to achieve it.
• An upgrading unit has several variables, and it is not easy to oversee the influence of each of them
in the system as a whole. The use of the tool can help the user to analyze the options when changing
operating parameters in the system.
• The possibility to upgrade biogas to use it as transportation fuel places biogas as an essential
alternative to unlink the transport sector from fossil fuels.
• Another possibility that biogas possesses is the energy storage capability either by compressing it to
pressures up to 300 bar or by cooling it down to its liquid state. Both technologies are proven and
used today in the natural gas sector. This storage can help the unlinking challenge between
production and consumption to be successfully achieved.
• Upgrading units open flexibility doors to biogas systems and might prove essential to the
implementation of strategies in the decarbonization of the economy.
11.2 Proposed Further Work

There are several aspects of the tool can be improved and complemented
• Adjust the model to real data operation.
• Run a detailed and structured sensitivity analysis of scrubber model to identify the most sensitive
parameters so the testing can be performed using this analysis as the guiding structure.

• Include the calculation of dimensions of the stripper since the procedure is the same to the one used
for the scrubber. The operating conditions of the stripper are included in the range tested by (Billet,
1995).
• Adjust and analyze the CH4 absorption model accurately to fit the process.
• Optimize the running time of the tool by:
o Implementing a fast solving approach to iterative over the equation solution for the holding
point.
o Implementing an efficient tear solving method for the closed-loop system of equations of
the flash tank.
o Reducing to a minimum the interaction between VBA and the excel sheets.
o Accessing the properties of the components by implementing a fast-access database solution
methodology.
o Implementing a fast-convergence methodology for the flash iteration procedure.
o Implementing an efficient numerical integration method to solve the NTU function.
o Implementing a predictive solving method for the height iteration function.
• Include pressure drop calculation for the scrubber, accessory equipment like filters and similar, and
for piping and accessories like elbows, tees, and similar.
• Include water vapor pressure for the vapor phase to increase accuracy.
• Include the chemical reaction of CO2 in water to calculate temperature changes and introduce
energy balancing equations.
• Implement “set of runs” in an interface that is user-friendly. This feature can help the designer
analyze the behavior of the system by giving several sets of operating conditions and obtaining the
reported results as desired.
• Add cost calculations for operation and investment for any given upgrading system.

References
Allegue, L. B. & Hinge, J., 2011. Report - Biogas and bio-syngas upgrading, Århus: Danish
Technological Institute, pp. 36.
Andersson, L.-N. P. & Sag, J. J., 2016. Biogasuppgradering - En studie om uppgraderingstekniker av
biogas, Stockholm: KTH - Royal Institute of Technology, pp. 35.
Andriani, D., Atmaja, T. D., Saepudin, A. & Wresta, A., 2014. A Review on Optimization Production
and Upgrading Biogas Through CO2 Removal Using Various Techniques. Applied Biochemistry
and Biotechnology, 172(4), pp. 1909-28.
Aspen Technology, Inc, 2017. Aspen Plus 9.0. Bedford, Massachusetts, USA.: Aspen Technology, Inc.
Bäbler, M. U., 2017. Lecture Script - Separation Processes for the Process Industry and the
Environment. Course KE2180. Stockholm: Department for Chemical Engineering and
Technology. KTH Royal Institute of Technology.
Bauer, F., Hulteberg, C., Persson, T. & Tamm, D., 2013. Biogas Upgrading - Review of Commercial
Technologies. (SGC Rapport; Vol. 270)., Lund: Svenskt Gastekniskt Center AB, pp. 36.
Billet, R., 1995. Packed Towers in Processing and Environmental Technology. New York: VCH
Publishers. pp. 31-146.
Billet, R. & Schultes, M., 1999. Prediction of Mass Transfer Columns with Dumped and Arranged
Packings. Updated Summary of the Calculation Method of Billet and Schultes. Institution of
Chemical Engineers, 77(Part A), pp. 498 - 504.
Biosling AB, 2012. Biosling product sheet 2012 - A new plant system for biogas upgrading on a small
scale, farm size level, Jukkasjärvi: Biosling AB.
BP, 2017. BP Statistical Review of World Energy 2017. [Online]
Available at: https://www.bp.com/en/global/corporate/energy-economics/statistical-review-
of-world-energy.html
[Accessed 04 02 2018].
Budzianowski, W. M., 2017. Energy Efficient Solvents for CO2 Capture by Gas-Liquid Absorption.
Cham, Switzerland: Springer International Publishing AG, pp. 4-9.
Budzianowski, W. M. & Brodacka, M., 2017. Biomethane storage: Evaluation of technologies, end
uses, business. Energy Conversion and Management, Volume 141, pp. 254-273.
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 Conversion and Management, Volume 141, pp. 2 - 19.
Carroll, J. J., Slupsky, J. D. & Math, A. E., 1991. The Solubility of Carbon Dioxide in Water at Low
Pressure. Journal of Physical and Chemical Reference Data, 20(6), pp. 1201-1209.
Cheguide, 2016b. Database k Components. [Online]
Available at: CheGuide.com
[Accessed 15 03 2018].

Cheguide, 2016. Binary Interaction Parameter (BIPS) by Regression (PR EOS). [Online]
Available at: https://cheguide.com/tag/peng-robinson/
[Accessed 20 03 2018].
Cheremisinoff, N. P., 2000. Handbook of chemical processing equipment. First ed. Boston:
Butterworth-Heinemann, pp. 244-320.
Cheric. Chemical Engineering and Materials Research Information Center, n.d. KDB Project. [Online]
Available at: https://www.cheric.org/research/kdb/
[Accessed 05 03 2018].
Cozma, P. et al., 2015. Modeling and Simulation of High-Pressure Water Scrubbing Technology
Applied for Biogas Upgrading. Clean Technologies and Environmental Policy, 17(2), p. 373–
391.
Crittenden, J. C. et al., 2012. MWH’s Water Treatment: Principles and Design. Third ed. Hoboken,
New Jersey: John Wiley & Sons, Inc.
Deublein, D. & Steinhauser, A., 2011. Biogas from Waste and Renewable Resources. Second ed.
Mörlenbach: Wiley-VCH Verlag GmbH.
Dortmund Data Bank, n.d. PCP - Pure Component Properties. [Online]
Available at: http://www.ddbst.com/ddb.html
[Accessed 05 03 2018].
Dupnock, T. L. & Deshusses, M. A., 2017. High-Performance Biogas Upgrading Using a Biotrickling
Filter and Hydrogenotrophic Methanogens. Applied Biochemistry and Biotechnology, 183(2),
pp. 488-502.
Enefalk, T. & Ersöz, T., 2016. Optimal rening av biogas för småskalig produktion och användning. En
studie om energioptimering av biogasanläggningar, Stockholm: KTH - Royal Institute of
Technology.
Hanlon, P., 2001. Compressor Handbook. New York: McGraw-Hill.
Houghton, G., McLean, A. M. & Ritceie, P. D., 1956. Compressibility, fugacity, and water-solubility of
carbon dioxide in the region 0-36 atm. and 0-100°C. Chemical Engineering Science, Volume 6,
pp. 182 - 187.
Houghton, G., McLean, A. M. & Ritceie, P. D., 1957. Compressibility, fugacity, and water-solubility of
carbon dioxide in the region 0-36 atm. and 0-100°C. Chemical Engineering Science, Volume 6,
pp. 132 - 137.
Hoyer, K. et al., 2016. Biogas Upgrading - Technical Review, Stockholm: Energiforsk, pp. 28,29.
IEA Bioenergy, 2017. Task 37: Energy from Biogas. Plan Lists. [Online]
Available at: http://task37.ieabioenergy.com/plant-list.html
[Accessed 04 02 2018].
IRENA, 2016. Renewable Energy benefits: Decentralised Solutions, Abu Dhabi: The International
Renewable Energy Agency.
Kadam, R. & Panwar, N. L., 2017. Recent advancement in biogas enrichment and its applications.
Renewable and Sustainable Energy Reviews, Volume 73, pp. 892-903.
Kolev, N., 2006. Packed Bed Columns For Absorption, Desorption, Rectification and Direct Heat
Transfer. Amsterdam, The Netherlands: Elsevier. pp. 44 - 49.

Lems, R. & Dirkse, E., n.d. Small-scale biogas upgrading: Green gas with the DMT Carborex-MS®.
[Online]
Available at: https://www.dmt-cgs.com/papers/
[Accessed 21 02 2018].
Luo, G. et al., 2012. Simultaneous Hydrogen Utilization and In Situ Biogas Upgrading in an Anaerobic
Reactor. Biotechnology and Bioengineering, 109(4), pp. 1088-1094.
Luque, R. & Lin, C. K. S., 2016. Handbook of Biofuels Production. Second ed. Duxford, UK: Woodhead
Publishing, pp. 3-12.
Microsoft Corporation, 2016. Visual Basic for Applications. Microsoft Excel for Microsoft Office 365
(16.0). Redmond, Washington, USA.: Microsoft Corporation.
NIST, 1998. Thermodynamic Properties of Water: Tabulation from the IAPWS Formulation 1995 for
the Thermodynamic Properties of Ordinary Water Substance for General and Scientific Use,
Boulder, Colorado, USA: NIST - National Institute of Standards and Technology.
Nock, W. J., Walker, M., Kapoor, R. & Heaven, S., 2014. Modeling the Water Scrubbing Process and
Energy Requirements for CO2 Capture to Upgrade Biogas to Biomethane. Industrial &
Engineering Chemistry Research, 53(32), pp. 12783-12792.
Olugasa, T. T. & Oyesile, O. A., 2015. Design and Construction of a Water Scrubber for the Upgrading
of Biogas. Fundamentals of Renewable Energy and Applications, 5(6:190), pp. 1-6.
Ong, M. D., Williams, R. B. & Kaffka, S. R., 2014. DRAFT Comparative Assessment of Technology
Options for Biogas Clean‐up, Davis: California Biomass Collaborative, pp. 76-78.
Raschig Gmbh, 2018. Raschig Super-Pak - Product Bulletin 501 - A new packing structure with
innovative advantages, Ludwigshafen: Raschig Jaeger Technologies.
Rearmer, H. H., Olds, R. H., Sage, B. H. & Lacey, W. N., 1944. Phase Equilibria in Hydrocarbon
Systems. Methane-Carbon Dioxide System in the Gaseous Region. Industrial and Engineering
Chemistry, 36(I), pp. 88 - 90.
Rogstrand, G., 2018. Record biomap project: introduction and objectives. Töreboda, RISE.
RVT Process Equipment GmbH, n.d. Highflow® Ring Plastic. [Online]
Available at: http://www.rvtpe.com/hiflow-ring-plastic/?lang=en
[Accessed 15 08 2018].
Sander, R., 2015. Compilation of Henry’s law constants (version 4.0) for water as solvent.
Atmospheric Chemistry and Physics, Volume 15, p. 4399–4981.
Sibiya, N. T., Muzenda, E. & Mbohwa, C., 2017. Evaluation of Potential Substrates for Biogas
Production via Anaerobic Digestion: A Review. Proceedings of the World Congress on
Engineering and Computer Science, Volume II, pp. 583-588.
Sofer, S. S. & Zaborsky, O. R., 1981. Biomass Conversion Processes for Energy and Fuels. First ed. New
York: Plenum Press, pp. 279.
Sölken, W., 2018. Distillation Columns: Column Internals. [Online]
Available at: http://www.wermac.org/equipment/distillation_part2.html
[Accessed 16 02 2018].
Sundberg, M., 2018. Gusum Lidkoping Biogas Plant Visit [Interview] (23 March 2018).

Toledo-Cervantes, A., Estrada, J. M., Lebrero, R. & Muñoz, R., 2017. A comparative analysis of biogas
upgrading technologies: Photosynthetic vs physical/chemical processes. Algal Research,
Volume 25, pp. 237-243.
VALORGAS, 2011. Evaluation of potential technologies and operational scales reflecting market needs
for low-cost gas upgrading systems (D5.1) in Valorisation of food waste to biogas, s.l.:
VALORGAS.
Valtra, 2018. Valtras Dual Fuel-traktorer – det naturliga valet. [Image]. [Online]
Available at: http://www.valtra.se/Valtras-Dual-Fuel-traktorer_2104.aspx
[Accessed 23 08 2018].
Vereinigte Füllkörper-Fabriken GmbH & Co. KG, 2016. Brochure: Your expert for tower packings,
catalyst support material and column equipment, Ransbach-Baumbach: Vereinigte
Füllkörper-Fabriken GmbH & Co. KG.
Vömel, H., 2011. Saturation vapor pressure formulations. [Online]
Available at:
https://www.eas.ualberta.ca/jdwilson/EAS372_13/Vomel_CIRES_satvpformulae.html
[Accessed 23 08 2018].
Wagner, W. & Kretzschmar, H.-J., 2008. International Steam Tables. Properties of Water and Steam
Based on the Industrial Formulation IAPWS-IF97.. 2nd ed. Berlin: Springer.
Wellinger, A., Murphy, J. & Baxter, D., 2013. The biogas handbook: Science, production and
applications. First ed. Cambridge: Woodhead Publishing Limited, pp. 22-34, 354, 362.
Xiaohong, Y., Shunxi, Z. & Weiling, Z., 2017. A new model for the accurate calculation of natural gas
viscosity. Natural Gas Industry B, Volume 4, pp. 100-105.


Small-Scale Biogas High Pressure Water Upgrading

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KTH Industrial Engineering

Small-Scale Biogas Upgrading System Modeling Tool

Master of Science Thesis

KTH – Royal Institute of Technology

Master of Science Thesis TRITA-ITM-EX 2018:625

Small-Scale Biogas Upgrading System Modeling Tool

KTH – Royal Institute of Technology

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Abbreviations and Symbols .......................................................................................................................................10

List of Tables ..............................................................................................................................................................17

2 Upgrading Techniques .......................................................................................................................................27

3 Water Scrubbing Columns .................................................................................................................................41

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3.2.1.1 Loading Point ..................................................................................................................................... 49

4 Upgrading Cycle Calculation ..............................................................................................................................65

5 Internal Energy Consumption ............................................................................................................................72

6 Model Implementation in VBA ..........................................................................................................................76

7 Model Comparison ............................................................................................................................................82

8 Sensitivity Analysis ............................................................................................................................................91

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10 Sustainability Analysis .....................................................................................................................................101

11 Conclusions and Further Work ........................................................................................................................106

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Abbreviations and Symbols

AD Anaerobic digester, anaerobic digestion

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𝑎 Species “a”. Also: Absorption column

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𝛼 Variable used in the calculation of the Peng-Robinson equation of state

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Table 1 Typical raw biogas characterization (Wellinger, et al., 2013)

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1.2 Problem Formulation

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1.6 Problems and Limitations

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1.7 Expected Outcomes

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2.1 Physicochemical Upgrading Systems

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2.1.1.2 Bubble-plate Towers

2.1.1.3 Spray Towers

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Figure 10 Structured packing. Images obtained from (Raschig Gmbh, 2018).

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2.1.3 Membrane Permeation

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Figure 13 Gas - Liquid membrane technique.

2.1.4 Cryogenic Distillation