Article

pubs.acs.org/EF

Upgrading Biogas to Biomethane Using Membrane Separation

Veronika Vrbová* and Karel Ciahotný
Department of Gaseous and Solid Fuels and Air Protection, University of Chemistry and Technology Prague, 166 28 Prague 6,
Prague, Czech Republic

ABSTRACT: Biogas contains carbon dioxide in the range of 35−45 vol %. Upgrading biogas to biomethane is primarily based
on carbon dioxide removal. Biomethane is essentially purified biogas that contains at least 95 vol % methane and it can be either
used as fuel for vehicles running on compressed natural gas (CNG) or injected into the natural gas grid. Nowadays, various
techniques are used for CO2 removal from biogas. Among the most commonly used technologies are adsorption, absorption,
cryogenic separation, and membrane separation. Currently, in the Czech Republic, no units for biogas upgrading to biomethane
are operating. In addition, during the summer months, there is heat overproduction from the co-generation units. In this work, a
Downloaded from pubs.acs.org by PANJAB UNIV on 01/27/19. For personal use only.

suitable unit for carbon dioxide separation is proposed. Carbon dioxide separation is possible using membrane separation. Along
with carbon dioxide, minor compounds present in biogas such as hydrogen sulfide and water are also separated. The
implementation of this unit makes it possible to obtain biomethane form biogas. Membrane separation was tested in a pilot scale
using real biogas. All experimental tests were conducted at the Central Waste Water Treatment Plant in Prague. Experimental
tests were performed using different types of membranes. For comparison purposes, the following membrane modules materials
were chosen: polysulfone and polyimide fiber membranes. Separation of moisture and trace compounds present in biogas was
tested for these two types of membrane materials. Other tests were performed using polyimide membranes. Parallel connection
of membrane modules was the most effective to remove carbon dioxide from biogas. Purified biomethane contained at least
Energy Fuels 2017.31:9393-9401.

95 vol % of methane, as is required, even when the highest flow rate was applied of 7 m3 h−1 of biomethane (measuring
conditions: 0.6−0.8 MPa). This small membrane separation unit is recommended for biogas units in wastewater treatment
plants.

1. INTRODUCTION The most common technological processes for biogas

The Czech Republic has a high biogas production potential, upgrading to biomethane are pressure swing adsorption (PSA),
absorption, membrane separation, and cryogenic separation.
primarily biomethane, as a natural gas substitute. Biogas
Adsorption and absorption unit generally have high energy
generated from the anaerobic digestion of agricultural products
demands and require relatively large equipment. In contrast, CO2
represents ∼25% of all bioenergy produced in the Czech
membrane separation is among the technologies with lower
Republic. Currently, there are over then 500 biogas station with a
energy demands. In addition, the equipment for membrane
total installed capacity of 360 MW. Biogas is usually burned in co- separation technologies is less voluminous.
generation units that are used for combined heat and power Recent research uses two PSA units connected in series. From
generation. Low heat consumption is observed during the the first PSA unit, one obtains biomethane and gas rich in carbon
summer. For this reason, technologies for the biogas upgrading dioxide. The gas stream rich in carbon dioxide is used as a feed
to the biomethane are being developed. stream for the second PSA unit. The output stream from the
Biogas composition is dependent on the organic substrate and second unit consists of very pure carbon dioxide (≥99%).
digestion conditions. Depending on the production parameters, Carbon dioxide can be subsequently used as a carbon source in a
landfill gas, biogas from agricultural biogas plants, or biogas from variety of chemical and biochemical processes.6−8 Among the
sewage sludge is generated. The typical biogas is a mixture mentioned biogas upgrading methods, membrane separation
containing methane, carbon dioxide, and many other compo- using polymer membranes is the most competitive one.
nents. Minor biogas components include water, hydrogen However, note that polymer membranes are very susceptible
sulfide, nitrogen, oxygen, and small amounts of ammonia. The to degradation caused by a series of compounds present in
calorific value of biogas is lower, because of the presence of biogas. Among the impurities that have the most adverse effect
carbon dioxide. The presence of the listed minor components are ammonia, hydrogen sulfide, and water. In order to prolong
causes corrosion or clogging of the engines for biogas membrane service lifetime, hydrogen sulfide removal and drying
combustion. Therefore, biogas purification to biomethane is are recommended.9,10 Currently, in the Czech Republic, no units
often performed. One of the primary utilizations of biogas is that upgrade biogas to biomethane are operating. Therefore, the
combustion in co-generation units, where the combined objective of this work consisted of proposing a suitable
production of heat and electricity occurs. During the summer membrane separation unit that can be implemented in a small
months, heat consumption decreases and, hence, excess heat is
released in the air. As a result, it is convenient to convert the Received: January 11, 2017
produced gas to biomethane. The methane content in bio- Revised: August 11, 2017
methane is >95%, making it a suitable biofuel for vehicles.1−5 Published: August 17, 2017

© 2017 American Chemical Society 9393 DOI: 10.1021/acs.energyfuels.7b00120

Energy Fuels 2017, 31, 9393−9401
Energy & Fuels Article

Table 1. Comparison of Technologies for Biogas Upgrading

process technology description advantages disadvantages
adsorption CO2, higher CxHy, H2S, Si-, F-, Cl- compounds and odorous compounds removed • high-quality gas • needs H2S removal
via activated carbon/carbon molecular sieves • dry process • 3−4 adsorption
columns
• no chemicals • CH4 quality is not
stable
• no wastewater • complicated
process
• partial N2 and O2 removal • higher investment
costs
• no bacterial contamination in • high energy
waste gas demands
• certified technology • large equipment

chemical and physical CO2 a H2S are absorbed in the scrubbing medium (e.g., water, ammines, glycols, • high-quality gas • wastewater
absorption etc.) liquidation
• suitable investment costs • high water
consumption
• no need for gas purification • higher investment
prior to the process costs
• compact process • high energy
demands
• certified/tested technology • large equipment
• it is possible to reuse CO2

membrane separation CO2 separation based on different compound permeability through the membrane • dry process • gas prepurification
needed
• no chemicals • higher methane
losses
• low mechanical deterioration • unstable long-term
behavior
• compact process

cryogenic separation CO2 is liquefied, because of high pressure and low temperature • high-quality gas • gas prepurification
needed
• no chemicals • very high energy
consumption
• no water • high investment
cost
• compact process • complicated
process
• it is possible to reuse CO2

biogas station. Moreover, the proposed unit should be financially was fed to the biomethane storage cylinder. Biomethane from the
feasible. cylinder then could be used directly as automobile vehicle fuel.
During the past years, membrane separation, compared to
other technologies, has become very competitive. Membranes 2. THEORY
have a series of applications such as potable water production,
wastewater disposal, gas purification, etc. Membrane processes Membrane separation is a highly selective process based on the
have very high separation efficiency and usually produce very- different transport rates of chemical species through the
high-purity retentate.11,12 membrane interphase. The main drawback of membrane
Several published works describe biogas upgrading to separation is low membrane resistance to aggressive compounds
biomethane via membrane separation. Scholz et al.13 stated present in the separated medium. The key parameters of porous
that the main advantage of membrane separation is its utilization membranes are pore size and shape, and transport flow through
under very severe operating conditions, such as high pressure (up the membrane interphase is dependent on pore size and shape,
to 2.5 MPa) and the presence of aggressive compounds layer porosity, and the interaction between pore walls and the
(hydrogen sulfide and water vapor). Baker et al.14 researched separated compounds.15
multistage separation, i.e., the utilization of various membranes
In Table 1, a comparison of the various carbon dioxide removal
to obtain high-purity biomethane.13,14 This work was based on
technological processes and subsequent biogas upgrading by
these two researches. In order to prolong membrane longevity, a
biogas precleaning step was proposed. Precleaning was Ryckebosch et al. and Wellinger et al. are depicted. From the
performed using silica gel and impregnated activated carbon summary emerges the conclusion that apparatus simplicity, setup
sorbents. Silica gel served for water removal, while impregnated demands, and reliability are the main advantage of CO2
activated carbon served for hydrogen sulfide removal. After membrane separation from biogas. The advantages of membrane
membrane separation, the retentate was then compressed via a separation are particularly evident in small biogas plants
three-stage compressor to 25 MPa. The compressed biomethane applications.16−18
9394 DOI: 10.1021/acs.energyfuels.7b00120
Energy Fuels 2017, 31, 9393−9401
Energy & Fuels Article

Table 2. Permeability and Selectivity of Polymeric Membranes for Gas Separationa

Permeability at 30 °C (Barrer)b
polymer H2 N2 O2 CH4 CO2 selectivity, CO2/CH4 Tg [°C]
cellulose acetate (CA) 2.63 0.21 0.59 0.21 6.30 30.0 80.0
ethyl cellulose (EC) 87.0 8.40 26.5 19.0 26.5 1.39 43.0
polycarbonate (PC) 0.18 1.36 0.13 4.23 32.5 150
polydimethylsiloxane (PDMS) 550 250 500 800 2700 3.38 −123
polyimide (PI) 28.1 0.32 2.13 0.25 10.7 42.8 317
polymethylpentene (PMP) 125 6.70 27.0 14.9 84.6 5.75 30.0
polyphenyloxide (PPO) 113 3.81 16.8 11.0 75.8 6.89 210
polysulfone (PSf) 14.0 0.25 1.40 0.25 5.60 22.4 190
a
Data taken from ref 28. b1 Barrer = 10−10 cm3 (STP) cm cm−2 s−1 cmHg−1.

2.1. Materials. The most common materials able to separate elevated pressure, and pore contamination. Both phenomenona
CO2 and CH4 are polymers or inorganic materials. In practical are key disadvantages of other membrane materials that are
applications, polymer membranes are the most common. The commonly used for biogas upgrading.27
separation efficiency is dependent on the polymer molecular Membrane fiber materials used for gas separation technologies
structure and the so-called “solubility−diffusion mechanism”. As can be divided in three main categories: polymer membranes,
a result, higher gas solubility and conductivity leads to higher inorganic membranes, and mixed-matrix membranes. Polymer
permeability through the membrane interphase. Gas flow membranes are the most commonly used membranes for gas
depends on the membrane effective surface area and driving separation, because of their low cost, simple production, and high
permeability force, i.e., concentration gradient across the stability when operating at higher pressure. The most common
membrane walls.19,20 polymer materials are cellulose acetate, polyimide, polysulfone,
The most commonly used membranes are made of polyimide, and polysiloxane. Inorganic membrane materials, such as
polyamide, and cellulose acetate. These membrane materials are ceramics and metal membranes, are still in the research stages.
very susceptible to moisture content; therefore, biogas should Mixed-matrix membranes are membranes that consist of a
always undergo drying prior to membrane separation.13,21 combination of polymer matrix and inorganic additives.
Aromatic polyimides are formed by aromatic rings and Polymer membranes used in most commercial applications
functional groups, which behaves similar to molecular sieves. work based on the dilution-diffusion mechanism. Depending on
Because of the high glass-transition temperature and low the polymer material, the permeability and selectivity of
solubility of the polymer, it is possible to use it in a wide range membranes differ. In Table 2, the selectivity of various
of pressures and temperatures. Polyimide also has excellent membrane materials based on the size of gas molecules is
chemical resistance.22 depicted. Gas permeability is highly influenced by dilution, which
A different class of membranes is made of polysulfone, is dependent on the ability of molecules to condense. The choice
polyetheramide, or polyethylenimide. Polysulfones contain a of the most suitable membrane material for a given gas separation
sulfonic group (OSO). The polymer chains are composed process is dependent on the membrane costs, selectivity,
of aromatic rings, which are linked by sulfol groups. Polysulfones permeability, chemical and mechanical stability, material
are able to withstand water, weak acids, and alkalis. availability, glass-transition temperature, and thermal stability.28
The embedding of ionic liquid in the membrane pores appears 2.2. Membrane Modules. Membranes are divided into
to be very promising. The main advantages of these membranes three categories: symmetric (homogeneous), asymmetric
are high flow permeability and high selectivity. It has been proven (heterogeneous), and composite. Symmetric membranes consist
that ionic liquids are primarily selective for methane and carbon of a single material. Membrane thickness varies from a few tenths
dioxide mixtures. However, currently, this class of membranes is of a millimeter to millimeter scale. Asymmetric membranes
too expensive for industrial applications. In addition, because of a consist of a series of very thin active layers. Each layer has a
membrane’s hygroscopic properties, humid environments cause thickness ranging from a few tenths to tens of micrometers. The
fast property losses. Even though membranes have low chemical active layer is placed on a thicker porous support layer of the
reactivity, membrane fouling still occurs, even for biogas same material. The porous layer can be up to a few millimeters
containing only trace amounts of impurities. As a result, ionic thick. When using asymmetric membranes, separation occurs
liquid membranes are not suitable for CO2 separation from only in the active layer. The thicker porous layer serves only to
biogas at an industrial scale.23 improve the mechanical properties of the membrane. Composite
A series of studies have been conducted in the framework of membranes are made from several types of materials. When using
membrane development technologies to assess options for composite membranes, separation also occurs in the active layer.
membrane fouling reduction. However, the proposed measures Several interlayers can be placed between the support and the
reduce the gas flow rate through the membrane walls. active layer.29
Polyethersulfone is a possible membrane material to obtain Membrane modules consist of a membrane placed into a
membranes that are chemically resistant, thermally stable and capsule. The modules are divided in two components: planar and
with high mechanical strength. Moreover, carbon-based tubular. Planar modules include hollow fiber module and spiral
membranes have been tested and showed higher selectivity, wound configurations. Spiral wound membranes contain several
compared to polymer materials.24−26 membrane envelopes and feed spacers wrapped around a central
Polydimethylsiloxane (PDMS) is a commonly used mem- collection pipe. Each pair of membranes is attached to the
brane material. PDMS is a stable, dense, and nonporous material. permeate tube and glued together. Gas feed injection is in the
PDMS-based membranes prevent bubble formation, at slightly direction of the central axis of the tube. Permeate passes across
9395 DOI: 10.1021/acs.energyfuels.7b00120
Energy Fuels 2017, 31, 9393−9401
Energy & Fuels Article

Table 3. Biomethane Quality Requirements for Vehicle Fuel Utilization According to Czech Standard Č SN 65 6514a
required biomethane value (according to Czech real biomethane
requirement Standard Č SN 65 6514) value notes
methane min 95.0 mol % min 95.0 mol % safety margin in the number of membranes
hydrogen sulfide ≤10 mg m−3 ≤10 mg m−3 unless gas is pretreated, removal prior to membrane access via
adsorbents is necessary
content
CO2 + N2 + O2 max 5 mol % max 5 mol % max 5 mol %
CO (max 2.5 mol %) max 3 mol % max 3 mol %
N max 1 mol % max 1 mol %
O max 2 mol % max 2 mol %
H2O content max 32 mg m−3 max 32 mg m−3 unless gas is pretreated, drying is necessary prior to membrane
access
a
Data taken from ref 31. Temperature at which, under an operating pressure of 4 MPa, water condenses from gaseous phase to liquid phase.
Temperature at which, under operating pressure, hydrocarbons condense from gaseous phase to liquid phase.

the membrane surface perpendicular to the center of the tube The contents of methane, higher hydrocarbons, carbon dioxide,
from where it subsequently exits.27 Tubular modules involve a nitrogen, and oxygen in the real biogas samples before membrane testing
series of modules consisting of various size tubules, such as was determined via gas chromatography (GC) (Model GC HP 5890,
tubular (diameter of 4−20 mm), capillary (diameter of 1.5−4 Agilent). The hydrogen sulfide and total sulfur contents were
determined using a GC system (Model GC HP 7890A, Agilent) that
mm), and hollow-fiber (diameter of <1.5 mm). was coupled with a sulfur chemiluminescence detector (Model SCD
2.3. Membranes of UBE Group. UBE membrane modules 355, Agilent). Retentate and permeate gas composition from the
are composed of polyimide membranes, which are produced by membrane modules was determined using the same chromatographic
condensation polymerization of biphenyl tetracarboxylic dia- methods. The online contents of methane, carbon dioxide, oxygen, and
nhydride and aromatic diamines. Polyimide membranes are a sulfur in the retentate and permeate were determined using a portable
type of hollow fiber module with an asymmetric structure, where analyzer (Sewerin Multitech 540). The analyzer is equipped with an
the separation layer serves to separate the gas mixture and is electrochemical sensor to determine the hydrogen sulfide and oxygen
designed to be very thin to achieve a practical permeation range. content and with an infrared sensor to determine the methane and
The microporous structure of the membrane only enhances the carbon dioxide content. The relative humidity of the gas was determined
using a Testo 400 Probe.
surface density of the layer and practically does not affect the Carbon dioxide separation from real biogas was tested with two
separation of the gas. There is space between the molecules along different membrane modules. The first, which was a membrane module
which the gases pass. The gases are moved from the side with from Air Products (trademark name PRISM), had polysulfone fiber
higher partial pressure to the lower-pressure side, because of the membranes. The second, a membrane module from UBE, had
pressure difference.30 polyimide membrane fibers.30 The separation properties of the modules
were tested in the apparatus depicted in Figure 1 (presented later in this
3. EXPERIMENTAL SECTION work). In Table 4, the feed biogas composition was depicted. First, the
3.1. Methods. During membrane material selection for biogas
upgrading, attention should be paid, not only to carbon dioxide and Table 4. Biogas Composition
methane content, but also to hydrogen sulfide and water vapor content.
requirement input content of the determined compoundsa
Hydrogen sulfide and water vapor can cause problems during biogas
separation. Therefore, the membrane material should be chemically methane content 61−63 vol %
stable and resistant to the presence of these two compounds. Moreover, carbon dioxide content 37−39 vol %
the selected material must meet certain requirements, such as resistance oxygen content 0 vol %
to higher pressure and temperature. Note that the operational hydrogen sulfide content 70−100 mg m−3
temperature can sometimes exceed 50 °C.13 relative humidity 40%−50%
In the Czech Republic, quality requirements for biogas utilization as gas temperature 20−24 °C
vehicle fuel are established by Czech standard Č SN 65 6514. This a
standard is applicable for biomethane sellers. In Table 3, biomethane All values were determined at a pressure of 0.005 MPa and operating
quality requirements are depicted. In addition, in Table 3, a comparison temperature.
of the gas parameters, as specified by the standard, and the actual values
obtained from a biogas upgrading unit are depicted.31 influence of pressure on the carbon dioxide separation efficiency of the
Tests were performed at the Central Waste Water Treatment Plant in membrane was tested. The results are depicted in Table 5.
Prague, where biogas is produce by the anaerobic fermentation of In order to assess the optimal degree of biogas purification, depending
sewage sludge. For comparison purposes, the following membrane on the apparatus power, a series of experimental tests applying different
module materials were chosen: polysulfone fiber membranes (with types of connections were performed. It was observed that, at constant
trademark name PRISM, from Air Products) and polyimide fiber
membranes (Model CO-C07FH, from UBE, Japan). The membranes
Table 5. Comparison of the Concentration of Methane
were tested using real biogas to obtain biomethane. Based on the results
acquired from tests, both membrane materials proved to be suitable. between UBE and AIR Product Modules at Different
With both membranes, it was possible to reach a methane content of Pressures
>95 vol % in the retentate. The influence of pressure and biogas flow on
the carbon dioxide separation efficiency of the membrane modules was Methane Concentration (%)
tested. Furthermore, humidity was determined in the biogas and the modules 0.3 MPa 0.5 MPa 0.7 MPa
separated streams exiting each membrane module. Biomethane exiting
AIR Product 93.29 94.37 94.75
the polyimide membrane module had a lower moisture content. Hence,
polyimide membrane modules were subjected to further testing.30 UBE 95.00 94.89 95.50

9396 DOI: 10.1021/acs.energyfuels.7b00120

Energy Fuels 2017, 31, 9393−9401
Energy & Fuels Article

Figure 1. Biogas ugrading to biomethane apparatus scheme for parallel-connected membrane modules. [Legend: 1, oil-free compressor; 2, manometers;
3, needle valve; 4, biogas storage and pressure equilizing cylinder; 5, membrane modules; 6, gas meter; 7, gas analyzer; 8, moisture and temperature
probe; 9, oil free compressor; and 10, storage biomethane cylinder. Measurements were performed in the temperature range of 15−25 °C and pressure
was 0.6−0.8 MPa.]

pressure, increasing the flow decreased the membrane CO2 separation 4. RESULTS AND DISCUSSION
ability. Note that, based on biomethane quality requirements, at least
The objective of the work was to design equipment that would be
95% CH4 content should be reached. Taking into consideration
practical applications, it was possible to establish the best biogas-to-
available for biogas stations with a heat power of ∼1000 kW. The
biomethane production ratios. The acquired data showed that it was
separation of the hydrogen sulfide by membrane modules was
possible to produce a 6 m3 h−1 flow of biomethane of the required
also determined.
quality from biogas.
In order to evaluate the carbon dioxide removal efficiency by
3.2. Equipment. In Figure 1 depicts the experimental apparatus. Gas membrane separation, the concentrations of the components of
from the biogas pipe was situated after the gas heater was fed to the methane, carbon dioxide, oxygen, and sulfate in permeate and
apparatus via an oil-free rotary screw compressor (feature 1 in Figure 1). retentate were measured. The relative humidity and temperature
Feed gas was compressed to the desired pressure, ranging from 0.6 MPa in the biogas were monitored to influence the separation
to 0.8 MPa. Then, the compressed biogas was fed via a pressure throughout the measurement period. In previous testing of the
equalizing cylinder (feature 4 in Figure 1) to the membrane modules UBE membrane modules, literature indicated that a moderate
(feature 5 in Figure 1). The separation performance was tested for both increase in methane concentration on the permeate side was
series- and parallel-connected membrane modules. In Figure 1, parallel- observed at temperatures from 10 °C to 60 °C, but the
connected membrane modules were depicted. Retentates from the concentration of methane was unchanged on the retentate side.30
membrane modules were combined into a single stream. The retentate The experiments were conducted in the temperature range of
stream was conducted to the diaphragm gas meter (feature 6 in Figure 1) 10−25 °C. Therefore, it was not necessary to solve its minimal
via a needle valve. The diaphragm gas meter was used to determine the influence.
retentate volume, while the gas flow was set with the needle valve. The acquired data from the experimental tests was indicated
Retentate flow was adjusted so that the output gas methane that both membrane modules can be utilized for biogas
concentration would not fall below 95%. The permeate and retentate upgrading to biomethane. In both cases, the methane content
methane, carbon dioxide, oxygen and hydrogen sulfide contents were in the retentate was at least 95 vol %.
monitored via Sewerin gas analyzer (feature 7 in Figure 1). In Table 5, no substantial differences are observed between
Simultaneously, moisture and temperature were also monitored via both membrane modules. As a result, the membrane module
the Testo probe (feature 8 in Figure 1). The produced biomethane was from UBE was used for all of the following experimental tests.
subsequently compressed to 25 MPa, suing a three-stage oil-free Initially, the influence of pressure on carbon dioxide separation
compressor. was established. Based on the experimental results, a pressure of
Permeate from the membrane modules was also combined into a 0.7 MPa was applied for the subsequent tests. At 0.7 MPa, it was
single stream directed to the diaphragm gas meter (feature 6 in Figure 1) possible to achieve a methane content of >95 vol % in the
in order to determine gas volume. The methane, carbon dioxide, oxygen, retentate.32
and hydrogen sulfide contents were determined with a second Sewerin During the next experimental step, we examined whether the
gas analyzer (feature 7 in Figure 1). Permeate moisture and temperature three membrane modules exhibited the best gas flow to methane
were monitored via the Testo probe (feature 8 in Figure 1). Permeate content in the retentate (>95 vol %) ratio when they were series-
gas flow containing 25% methane was returned to the biogas pipe, connected or parallel-connected. The results obtained for each
where, after being mixed with raw biomethane, it was used as fuel in the module connection and retentate flow have been depicted in
co-generation units. The same experimental procedure also was applied Figures 2 and 5 (presented later in this work). Retentate flow was
for series-connected membrane modules. gradually regulated until reaching the maximum possible value of
9397 DOI: 10.1021/acs.energyfuels.7b00120
Energy Fuels 2017, 31, 9393−9401
Energy & Fuels Article

Figure 2. Dependence of methane content [vol %] on retentate flow for parallel-connected membrane modules.

Figure 3. Dependence of methane content [vol %] on retentate flow for series-connected membrane modules.

Figure 4. Hydrogen sulfide content in the retentate for parallel-connected membrane modules.

Figure 5. Hydrogen sulfide content in the retentate for series-connected membrane modules.

9398 DOI: 10.1021/acs.energyfuels.7b00120

Energy Fuels 2017, 31, 9393−9401
Energy & Fuels Article

7 m3 h−1. For this work, it was important to determine the applying series-connected membrane modules, even greater
parameters for equipment that produces a high amount of hydrogen sulfide decreases were observed, compared to parallel-
biomethane with a methane concentration of 95 vol %. connected membrane modules. In Figure 5 changes on hydrogen
Similar results were reported in the work of Harasimowicz et sulfide content for different retentate flow are depicted.
al.22 They tested the same membrane material but used a model When flow was set at the highest value retentate and the
gas mixture as the inlet gas. The focus of their work was the permeate was sampled in Tedlar gas sampling bags. The results
influence of gas flow on the final methane content in the from GC-FID/TCD analyses are depicted in Table 7.
retentate. Separation was performed at pressures under 0.58
MPa. In our work, separation was performed in the pressure Table 7. Composition of Each Individual Gas Stream at a
range of 0.6−0.8 MPa, using real biogas. Therefore, it was crucial Retentate Flow of 6.5 m3 h−1 and with Series-Connected
to determine the dependency of outlet methane content in the Membrane Modules
retentate on retentate gas flow. Another difference between the
two works is that real biogas also contains other minor feed retentate permeate
requirement compositiona compostionb compositionb
compounds, such as hydrogen sulfide and water. The presence
of minor compounds can cause slight differences on the final CH4 61.82 vol % 96.37 vol % 25.16 vol %
CO2 37.90 vol % 2.21 vol % 74.92 vol %
results. The inlet content of each individual compound is
N2 0.23 vol % 0 vol % 0 vol %
depicted in Table 4.
O2 0 vol % 0.34 vol % 0.39 vol %
Moreover, the influence of parallel and series membrane
H2S 36.43 mg m−3 9.11 mg m−3 21.25 mg m−3
module connection was tested. The results are depicted in a
Figures 2 and 3. In Figures 4 and 5, changes in the hydrogen All values were measured at a pressure of 0.005 MPa and operation
sulfide content with increasing flow of retentate gas can be temperature. bAll values were measured at pressures in the range of
0.6−0.8 MPa and operation temperature.
observed. To date, this effect has not been tested much in
available works.22
In Figures 2 and 3, for better visibility of methane content, the The final experimental step consisted of compressing the
y-axis value scale is presented from 90 vol % to 100 vol %. purified biomethane to 25 MPa in order to determine whether
In Figure 2, it can be observed that, when using parallel- the gas composition was consistent with the Czech Standard
connected membrane modules, the methane content did not Č SN 65 6514 requirements. After being compressed in a
decrease below 95 vol %, even at the highest flow rate. cylinder, biomethane was sampled and analyzed as described in
Another monitored parameter was hydrogen sulfide content in the previous experiments. In Table 8, a comparison between
the retentate stream. The input biogas hydrogen sulfide content biomethane composition and the standard requirements was
was in the range from 70 mg m−3 to 100 mg m−3. In Figure 4, it depicted.
can be observed that, when using polyimide membrane modules,
partial hydrogen sulfide separation occurred. Hydrogen sulfide Table 8. Compressed Purified Biomethane Composition
content in the retentate at the highest flow was ∼25 mg m−3. Ready for Utilization as Vehicle Fuel
When flow was set at the highest retentate value, the permeate required value real value
was sampled in Tedlar gas sampling bags. Samples were analyzed requirement biomethane (Č SN 65 6514) biomethanea
via GC coupled with thermal conductivity detection (TCD) and
methane min 95.0 mol % 96.72 mol %
flame ionization detection (FID) equipment. The results from
hydrogen sulfide ≤10 mg m−3 n.d.b
GC-FID/TCD analyses are depicted in Table 6.
content
CO2 + N2 + O2 max 5 mol % 3.27 mol %
Table 6. Composition of Each Individual Gas Stream at a
CO2 (max 2.5 mol %) 2.8 mol %
Retentate Flow of 7 m3 h−1 and with Parallel-Connected
N2 0.4 mol %
Membrane Modules
O2 0.07 mol %
retentate permeate a
All values were measured at pressure in the range 25 MPa and
requirement input contenta compositionb composition operational temperature. bNot detected.
CH4 61.82 vol % 96.37 vol % 25.16 vol %
CO2 37.90 vol % 2.21 vol % 74.92 vol %
N2 0.23 vol % 0 vol % 0 vol % 5. CONCLUSIONS
O2 0 vol % 0.34 vol % 0.39 vol %
H2S 100 mg m−3 21.25 mg m−3 72.86 mg m−3
The utilization of membrane separation for biogas upgrading to
a biomethane appears to be very interesting. Compared to other
All values were measured at a pressure of 0.005 MPa and at operation technologies that are currently used for biogas upgrading,
temperature. bAll values were measured at pressures in the range 0.6−
0.8 MPa and at operation temperature.
membrane separation possesses the advantage of being relatively
simple. Membrane separation does not require high operational
demands. However, the biggest disadvantage is higher invest-
When three membrane modules were series-connected, a ment costs.
decrease in methane content was observed with increasing flow. Biogas production, in order to be accessible for agricultural
At a retentate flow of 6.5 m3 h−1, the methane content decreased biogas plants, should be, first of all, inexpensive and simple. The
to <95 vol %. In Figure 3, the methane content changes, required energy to upgrade biogas to biomethane is a key
depending on retentate flow, are depicted. parameter when choosing the most suitable technology. Biogas
Hydrogen sulfide content in the retentate was simultaneously membrane separation is characterized by the production of very-
monitored. Also, partial hydrogen sulfide separation was high-purity biomethane. The produced biomethane, when
confirmed for series-connected membrane modules. When applying certain operation modes, can have a methane content
9399 DOI: 10.1021/acs.energyfuels.7b00120
Energy Fuels 2017, 31, 9393−9401
Energy & Fuels Article

of up to 99 vol %. In this work, by regulating the retentate flow, (9) Molino, A.; Migliori, M.; Ding, Y.; Bikson, B.; Giordano, G.;
one could achieve a methane content of >95 vol % in the Braccio, G. Biogas upgrading via membrane process: Modelling of pilot
produced biomethane. A methane content of >95 vol % was plant scale and the end uses for the grid injection. Fuel 2013, 107, 585−
achieved even at retentate flows as high as 7 m3 h−1. The 592.
produced biomethane met the requirements established by (10) Molino, A.; Iovane, P.; Migliori, M. Biomethane production by
Czech Standard Č SN 65 6514. Additional produced biomethane biogas with polymeric membrane module. Membrane Technol. Biorefin.
2016, 465−482.
can be compressed at 25 MPa. The compressed biomethane can (11) Holloway, R. W.; et al. Life-cycle assessment of two potable water
be used as automobile fuel for vehicles running on CNG or can reuse technologies: MF/RO/UV−AOP treatment and hybrid osmotic
be injected into the natural gas grid. The residual permeate membrane bioreactors. J. Membr. Sci. 2016, 507, 165−178.
contained up to 25 vol % CH4. Therefore, it was possible to (12) Alibardi, L.; et al. Anaerobic dynamic membrane bioreactor for
return it to the biogas pipe, where was mixed back with raw wastewater treatment at ambient temperature. Chem. Eng. J. 2016, 284,
biogas and used for electricity and heat production in the co- 130−138.
generation units. (13) Scholz, M.; Melin, T.; Wessling, M. Transforming biogas into
The experimental tests were performed using real biogas that biomethane using membrane technology. Renewable Sustainable Energy
contained 70−100 mg m−3 H2S and 40%−50% relative humidity. Rev. 2013, 17, 199−212.
In order to prolong membrane longevity, it is recommended to (14) Baker, R. W. Membrane Technology and Applications, 3rd Edition;
place an adsorption unit for hydrogen sulfide and water vapor Wiley−Blackwell: Oxford, U.K., 2012.
removal. Unfortunately, currently available research works focus (15) Scholes, C. A.; Stevens, G. W.; Kentish, S. E. Membrane gas
primarily on carbon dioxide membrane separation from biogas. separation applications in natural gas processing. Fuel 2012, 96, 15−28.
(16) Ryckebosch, E.; Drouillon, M.; Vervaeren, H. Techniques for
Therefore, the results presented in this work are of great transformation of biogas to biomethane. Biomass Bioenergy 2011, 35 (5),
importance for the design of future biogas membrane separation 1633−1645.
units.

■
(17) Wellinger, A.; Lindberg, A. Biogas Upgrading and Utilisation; Task
34: Energy from Biological Conversion of Organic Waste; IEA
AUTHOR INFORMATION Bioenergy: Paris, 2005.
Corresponding Author (18) Valenti, G.; Arcidiacono, A.; Nieto Ruiz, J. A. Assessment of
*E-mail: [email protected]. membrane plants for biogas upgrading to biomethane at zero methane
emission. Biomass Bioenergy 2016, 85, 35−47.
ORCID (19) Côté, P.; Bersillon, J.; Huyard, A. Bubble-free aeroration using
Veronika Vrbová: 0000-0002-3536-5005 membranes: mass transfer analysis. J. Membr. Sci. 1989, 47 (1−2), 91−
Notes 106.
The authors declare no competing financial interest. (20) Ahmed, T.; Semmens, M. J. The use of independently sealed

■
microporous hollow fiber membranes for oxygenation of water: model
ACKNOWLEDGMENTS development. J. Membr. Sci. 1992, 69 (1−2), 11−20.
(21) Baker, R. W.; Lokhandwala, K. Natural gas processing with
The results achieved in this paper were financially supported by membranes: an over-view. Ind. Eng. Chem. Res. 2008, 47 (7), 2109−
TAČ R Project No. TA03020421, “Technological Unit for 2121.
Limited Local Production of Biomethane Replacing Fossil (22) Harasimowicz, M.; et al. Application of polyimide membranes for
Fuels in Transportation and Agriculture”. The authors of this biogas purification and enrichment. J. Hazard. Mater. 2007, 144 (3),
paper would like to thank TAČ R for the financial support, as well 698−702.
as Central Waste Water Treatment Plant in Prague for creating (23) Poloncarzova, M.; Vejrazka, J.; Vesely, V.; Izak, P. Effective
the possibility to measure with real biogas. Purification of Biogas by a Condensing Liquid Membrane. Angew. Chem.

■
2011, 123 (3), 695−697.
REFERENCES (24) Guo, J.; Sotto, A.; Martin, A.; Kim, J.; et al. Preparation and
characterization of polyethersulfone mixed matrix membranes embed-
(1) Rasi, S.; Veijanen, A.; Rintala, J. Trace compounds of biogas from
ded with Ti- or Zr-incorporated SBA-15 materials. J. Ind. Eng. Chem.
different biogas production plants. Energy 2007, 32 (8), 1375−1380.
2017, 45 (25), 257−265.
(2) Starr, K.; Villalba, G.; Gabarrell, X. Upgraded biogas from
(25) Zhu, L.-J.; Zhu, L.-P.; Jiang, J.-H.; Yi, Z.; Zhao, Y.-F.; Zhu, B.-K.;
municipal solid waste for natural gas substitution and CO2 reduction −
Xu, Y.-Y.; et al. Hydrophilic and anti-fouling polyethersulfone
A case study of Austria, Italy, and Spain. Waste Manage. 2015, 38, 105−
116. ultrafiltration membranes with poly(2-hydroxyethyl methacrylate)
(3) Balat, M.; Balat, H. Biogas as a renewable energy sourceA review. grafted silica nanoparticles as additive. J. Membr. Sci. 2014, 451, 157−
Energy Sources, Part A 2009, 31, 1280−1293. 168.
(4) Molino, A.; Nanna, F.; Iovane, P. Low pressure biomethane (26) Haider, S.; Lindbråthen, A.; Hägg, M. Techno-economical
production by anaerobic digestion (AD) for the smart grid injection. evaluation of membrane based biogas upgrading system; a comparison
Fuel 2015, 154, 319−325. between polymeric membrane and carbon membrane technology. Green
(5) Iovane, P.; et al. Experimental test with polymeric membrane for Energy Environ. 2016, 1, 222.
the biogas purification from CO2 and H2S. Fuel 2014, 135, 352−358. (27) Kavousi, F.; et al. Hydrodynamics and gas transfer performance of
(6) Augelletti, R.; Conti, M.; Annesini, M. C. Pressure swing confined hollow fibre membrane modules with aid of computational
adsorption for biogas upgrading. A new process configuration for the fluid dynamics. J. Membr. Sci. 2016, 513 (1), 117−128.
separation of biomethane and carbon dioxide. J. Cleaner Prod. 2017, 140 (28) Basu, S.; Khan, A.; Cano-Odena, A.; Liu, C.; Vankelecom, I.
(3), 1390−1398. Membrane-based technologies for biogas separations. Chem. Soc. Rev.
(7) Xu, Y.; Huang, Y.; Wu, B.; Zhang, X.; Zhang, S.; et al. Biogas 2010, 39 (2), 750−768.
upgrading technologies: Energetic analysis and environmental impact (29) Palatý, Z. Membránové Procesy, 1st Edition; VŠCHT Praha:
assessment. Chin. J. Chem. Eng. 2015, 23 (1), 247−254. Prague, Czech Republic, 2012.
(8) Grande, C. A.; Blom, R. Utilization of dual-PSA technology for (30) UBE Group. Separation membrane UBE, 2012. CO2 separation
natural gas upgrading and integrated CO2 capture. Energy Procedia 2012, membrane. Available via the Internet at: http://www.ube.co.th/en/
26, 2−14. product-details.php?id=6, accessed March 5, 2017).

9400 DOI: 10.1021/acs.energyfuels.7b00120

Energy Fuels 2017, 31, 9393−9401
Energy & Fuels Article

(31) Č SN 65 6514. Automotive fuelsBiogas for positive (spark) ignition

engines requirements and test methods; Č eský Normalizačni ́ Institut:
Hradec Králové, Czech Republic, 2007; 10 pp.
(32) Vrbová, V.; Ciahotný, K.; Hádková, K. Separation of CO2 from
biogas by membrane modules. PALIVA 2014, 6 (3), 78−82.

9401 DOI: 10.1021/acs.energyfuels.7b00120

Energy Fuels 2017, 31, 9393−9401