Microporous and Mesoporous Materials 116 (2008) 504–512

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Microporous and Mesoporous Materials

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

Thermal stability of polyethylenimine based carbon dioxide adsorbents

and its influence on selection of regeneration strategies
T.C. Drage a,*, A. Arenillas b, K.M. Smith a, C.E. Snape a
a
Nottingham Fuel and Energy Centre, School of Chemical, Environmental and Mining Engineering, University of Nottingham, Nottingham NG7 2RD, UK
b
Consejo Superior de Investigaciones Cientificas Instituto Nacional del Carbon, Apartardo 73, 33080 Oviedo, Spain

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

Article history: Two approaches, thermal swing desorption over a range of temperatures and time in an atmosphere of
Received 8 June 2007 CO2 and using nitrogen as a stripping gas at elevated temperatures, are explored for the regeneration
Received in revised form 18 April 2008 of the polyethylenimine based adsorbents. Thermal swing regeneration was demonstrated to give good
Accepted 7 May 2008
cyclic regeneration capacities (2 mmol g1). However, further reaction of the regenerable carbamate ion
Available online 16 May 2008
to form urea linkages, significantly reduces cyclic capacity and therefore the lifetime of the adsorbent.
Regeneration of this secondary reaction product at elevated temperatures was attempted in a nitrogen
Keywords:
atmosphere, and whilst recovering some of the original capacity did not fully regenerate the adsorbent.
CO2 capture
Polymer stability
Adsorbent regeneration with nitrogen as a stripping gas was used as an alternative regeneration method,
Regeneration the results of which suggest that steam stripping may be a potential method for adsorbent regeneration.
Adsorption Crown Copyright Ó 2008 Published by Elsevier Inc. All rights reserved.

1. Introduction
Increasing awareness of the influence of greenhouse gases on
global climate has led to recent efforts to develop strategies for
the reduction of carbon dioxide (CO2) emissions. In 2000, the burn-
ing of coal generated 37.8% of all CO2 arising from fossil fuels [1]
and as a result the strategy that is receiving the most attention in-
volves the capture of CO2 from large point sources (such as fossil
fuel-fired power plants). The greenhouse gas can then be stored
long term, either underground or in the ocean. However, to eco-
nomically transport and store CO2 it must be in a relatively pure
high pressure form, requiring the separation and compression of
the CO2 emitted by the power plant.
The CO2 capture step is projected to account for the majority
(ca. 75%) of the expense for the overall carbon capture and subse-
quent storage process. Aqueous solutions of amines have long been
used by industry as absorbents for acid gas (CO2, H2S) removal, and
in fact provide a large percentage of the natural gas sweetening
operations. To date, all commercial CO2 capture plants use similar
processes based on chemical absorption with an aqueous alkanol-
amine solvent [2–4] of which monoethanolamine (MEA) is the
most popular [5]. However, regarding their application to flue
gases, these technologies need significant modification and this
ultimately leads to high capital and running costs. The typical en-
ergy penalty incurred by the operation of the MEA capture process
* Corresponding author. Tel.: +44 115 951 4099; fax: +44 115 951 4115.
E-mail address: trevor.drage@nottingham.ac.uk (T.C. Drage).
is an estimated 15–37% of the net power output of the plant [6].
Therefore, although amine technology could be suitable for flue
gases, the development of alternative low cost technologies could
be crucial in the long term to provide a more cost and environmen-
tally effective route to carbon capture and storage on a global scale.
Adsorption is considered to be a promising technology for the
efficient capture of CO2 from flue gases. Some of the most success-
ful adsorbents for the post-combustion capture of CO2 at close to
atmospheric pressure have been developed via the alteration of
the surface chemistry of porous substrates by functionalization
with amine groups. These adsorbents capture CO2 by the formation
of reversible chemical bonds. The reaction between CO2 and poly-
ethylenimine (PEI) is proposed to occur by the formation of a car-
bamate ion [7] and is similar to the absorption of CO2 with primary
alkanolamines [8]. The reaction is proposed to be a two stage reac-
tion, similar to that of CO2 absorption with amine solvents, with
two moles of amine reacting with one mole of CO2 by a zwitterion
mechanism, followed by base catalysed deprotonation via a second
amine group [9] to form a stable carbamate ion.
CO2 þ 2R2 NH $ R2 NHþ2 þ R2 NCOO ð1Þ
CO2 þ 2R3 N $ R4 Nþ þ R2 NCOO ð2Þ
The reaction is reversible, allowing for the adsorbent to be regen-
erated by thermal, vacuum or pressure swing adsorption cycles.
Example adsorbent materials include diethanolamine (DEA) upon
an acrylic ester polymer resin [10], tetraethylenepentaamineacrylo-
nitrile (TEPAN) upon non-ionic, polymeric polmethylmethacrylate
(PMMA) beads [11] and aminopropyltriethoxysilane bonded to

1387-1811/$ - see front matter Crown Copyright Ó 2008 Published by Elsevier Inc. All rights reserved.
doi:10.1016/j.micromeso.2008.05.009
 T.C. Drage et al. / Microporous and Mesoporous Materials 116 (2008) 504–512
silica gel [12]. Combinations of polyethylenimine (PEI) and polyeth-
ylene glycol (PEG) impregnated onto the surface of low cost fly ash
derived carbons [13,14] and MCM-41 [15,16] have also been applied
successfully.
Overall, the success of the adsorbents is dependent on the
development of a material that, at flue gas temperatures, has a high
CO2 selectivity and adsorption capacity. However, of equal impor-
tance is the ease of regeneration and the lifetime of the adsorbents.
The easier an adsorbent is to regenerate the more efficient the
overall capture process will become, for example reducing the
overall temperature required for regeneration or the steam
requirement for stripping. Similarly the lifetime of the adsorbent
is of importance in determining the rate of adsorbent replacement,
influencing the economics of the process. Previously it has been
demonstrated that adsorbents can be regenerated using vacuum
to facilitate pressure swing adsorption (PSA) with or without heat-
ing [7,17–19]. However, for the post-combustion capture and stor-
age of CO2 from power plant, the captured CO2 would need to be
pressurised before transportation and storage, resulting in a large
energy penalty. As a result it is considered that an alternative
regeneration method to PSA would be preferable. Regeneration of
PEI-loaded substrates isothermally (with respect to the adsorption
temperature), and at ambient pressure, has been achieved by sub-
jecting the sorbents to a flow of stripping gas, for example nitrogen
[20]. However, an exploration of the thermal swing adsorption
(TSA) cycles of PEI based adsorbents in an atmosphere of CO2
and its influence on adsorbent lifetime has, to the best of the
authors knowledge, yet to be published.
In this paper the thermal stability of PEI immobilised on a mes-
oporous silica support is described over a range of temperatures
and time in an atmosphere of air, CO2 and N2. TSA cycles are sim-
ulated using thermogravimetric analysis over a range of tempera-
tures to determine cyclic adsorption capacities. The use of TSA in a
stream of CO2 allows for the regeneration of the adsorbents and
production of a stream of pure CO2 without the need for further
separation processes. The lifetime of the adsorbents over numer-
ous TSA cycles has been assessed by long term exposure of the
adsorbents to CO2 at elevated temperatures using TGA and a spe-
cially constructed dynamic testing rig. To determine the reactions
responsible for degeneration of the adsorbent, post-test analysis
has been undertaken by diffuse reflectance infrared spectroscopy
(DRIFT), solid state 13C nuclear magnetic resonance (NMR) and X-
ray photoelectron spectroscopy (XPS). The regeneration of PEI
using nitrogen as a stripping gas at elevated temperatures has also
been explored and will be discussed as an alternative to TSA.
2. Experimental
2.1. Materials and adsorbent preparation
The adsorbents used throughout this study were synthesised by
the impregnation of a mesoporous silica supports with PEI. A pro-
prietary inorganic support with a BET surface area of approxi-
mately 250 m2 g1, pore volumes of 1.7 cc g1 and a mean pore
diameter of approximately 20 nm was used for the preparation
of the adsorbent. Textural characterisation was undertaken from
nitrogen adsorption and desorption isotherms obtained at 77 K
(Micromeritics ASAP 2010). Polyethylenimine (PEI) was supplied
in various molecular mass (MM) forms 423 linear, 600 and 1800
MM hyperbranched forms by Sigma–Aldrich, UK. PEI was incorpo-
rated into the support by a wet impregnation method [15,16]. A
known mass of PEI was dissolved in methanol, the dissolution of
which was aided by mechanically shaking the mixture for
15 min. A PEI loading of 40 wt.% was used throughout this study.
The required mass of proprietary inorganic support was added
505
and the resulting slurry was mechanically shaken for a further
30 min and subsequently dried overnight under reduced pressure
(ca. 700 mmHg) at 70 °C.
2.2. Measurement of PEI thermal stability
The stability of PEI and silica immobilised PEI in air, nitrogen
and CO2 over a temperature range of 25–200 °C was determined
using a TA instruments Q500 thermogravimetric analyser (TGA).
Approximately 10 mg of adsorbent was placed in a platinum cruci-
ble and heated to 100 °C in N2 atmosphere at a flow rate of
20 ml min1 and held isothermally for 0.5 h to remove any mois-
ture. The temperature was decreased to 25 °C and the gas switched
to either nitrogen, air or CO2 with a flow rate of 20 ml min1, these
conditions were maintained for 2 h. The temperature was then in-
creased gradually at a rate of 0.25 °C min1, the slow heating rate
allowing equilibrium to be attained, up to 200 °C with the weight
change of the adsorbent monitored throughout.
2.3. Adsorbent regeneration using thermal swing adsorption cycles
Simulation of a three cycle thermal swing adsorption (TSA) pro-
gramme in an atmosphere of CO2 to determine its effectiveness
and influence on adsorbent lifetime was performed by TGA. After
initially drying the adsorbent, 0.5 h in nitrogen at 100 °C, the tem-
perature was decreased to 75 °C and the gas flow, whilst being kept
at a constant flow rate of 20 ml min1, was switched to CO2.
Adsorption was performed at 75 °C for 1 h, to allow equilibrium
adsorption capacity to be achieved. The adsorption cycle was
immediately followed by desorption, by heating the adsorbent at
15 °C min1 to the desired regeneration temperature, between
110 and 180 °C, and held isothermally for 60 s. Both adsorption
and regeneration cycles were performed in an atmosphere of pure
CO2. After the short period of regeneration, the adsorbent was
cooled to 75 °C at 15 °C min1 to repeat the adsorption cycle. The
adsorption and regeneration cycles were repeated a further two
times to assess cyclic capacity and stability. Adsorption capacities
were calculated compared to the mass of adsorbent (mmol g1).
The adsorption capacities after the first and second regeneration
cycle are quoted as a percentage of the original adsorption capacity
to provide a clear indication of regenerated capacity. Numerous
regeneration cycles were simulated by increasing the regeneration
period to 1 h and monitoring the change in performance by an
adsorption cycle at 75 °C, before and after regeneration. The long
term effect of contact with CO2 with the adsorbent was undertaken
using a specially constructed dynamic testing rig (Fig. 1). The
adsorbents were placed in a stream of CO2 at 140 °C for up to
16 h, with a gas flow of 200 ml min1. Adsorption capacity was
determined by removing an aliquot of adsorbent from the reactor,
with adsorption capacity determined at 75 °C using TGA as
described for the TSA cycles.
2.4. Pre- and post-test analysis of adsorbents
Characterisation of the adsorbents before and after contact with
CO2 and subsequent regeneration was performed by elemental
analysis, solid state 13C nuclear magnetic resonance (NMR), diffuse
reflectance infrared spectroscopy (DRIFT) and X-ray photoelectron
spectroscopy (XPS).
The carbon, hydrogen and nitrogen content of the adsorbents
were determined with a Thermo 1112 Series Flash EA, with the
oxygen content determined by difference. Elemental analysis was
determined on a dry ash free basis corrected for moisture and inor-
ganic content by loss on ignition analysis conducted using TGA.
506 T.C. Drage et al. / Microporous and Mesoporous Materials 116 (2008) 504–512
Mass Flow
Controller
Sample Line
Solenoid
15% N2
CO2 mix
Fig. 1. Schematic of dynamic testing apparatus used for thermally assisted pressure swing desorption experiments.
Solid state 13C NMR spectra were obtained using a Bruker
DSX200 instrument equipped with double-bearing probes for cross
polarisation (CP) and magic angle spinning (MAS). The resonance
frequency for 13C was 50 MHz, the sample was spun at the magic
angle with a speed of 6.0 kHz. Typically ten thousand scans were
accumulated with high power 1H decoupling for the CP experi-
ments. For CP, the contact time was 3.0 ms and the relaxation delay
was 1.5 s. All spectra were obtained at ambient temperature and
processed with a line broadening factor of 50 Hz. Chemical shifts
were calibrated using an external sample of tetrakistrimethylsilane
(TKS).
Determination of the surface functionalities of the adsorbents
was undertaken by analysis with DRIFT spectroscopy. A Nicolet
Magna-IR 560 spectrometer was used for analysis with 128 scans
taken and at resolution of 4 cm1. Further characterisation of the
surface chemistry of the adsorbent was carried out by X-ray photo-
electron spectroscopy (XPS) on a Kratos AXIS ULTRA with a mono-
chromated A1 ka X-ray source (energy 1486.6 eV) operated at
15 mA emission current and 10 kV anode potential 150 W. The
ULTRA was used in FAT (Fixed Analyser Transmission) mode, with
pass energy 20 eV for high resolution scans. The magnetic immer-
sion lens system allows the area of analysis to be defined by aper-
tures, a ‘slot’ aperture of 300  700 lm for wide/survey scans and
high resolution scans. The high resolution scans were charge cor-
rected to the main C 1s peak = 284.8 eV. Elemental quantification
was corrected using a standard of indium wire and was used to
characterise different forms for carbon, nitrogen and oxygen.
2.5. Thermally assisted regeneration using nitrogen as a sweep gas
A specially constructed dynamic testing rig (Fig. 1) was used to
undertake regeneration of the PEI-based adsorbent using N2 as a
sweep gas. The rig is designed to accurately control gas flow rates
through the adsorbent contained in a packed bed whilst accurately
monitoring CO2 concentration in the gas stream. Approximately
3 g of adsorbent was loaded into the reactor and purged for
30 min in a stream of nitrogen. Complete saturation of the adsor-
bent was performed at 75 °C in a simulated flue gas of 15% CO2
in balance N2 at a flow rate of 100 ml min1 (gas residence time
of 0.5 s). Regeneration was performed at a range of N2 flow rates
(50–100 ml min1) and over a range of temperatures (75–140 °C).
The construction of the apparatus to incorporate a mass flow con-
troller allows for the accurate monitoring of the volume of N2 strip-
ping gas required to regenerate the adsorbent. The use of the blank
by-pass line allows for calibration of the CO2 meter to establish sat-
uration and complete regeneration of the adsorbent.
Oven
Blank Line
Analyser Vent
3. Results and discussion
3.1. Thermal stability of PEI determined by TGA analysis
The thermal stability of the supported and un-supported poly-
theylenimine (1800 MM) in nitrogen, air and CO2 up to 200 °C is
presented in Fig. 2, the silica support is stable over the same tem-
perature range (see Supplementary material). In an atmosphere of
air and nitrogen the mass of PEI impregnated adsorbent decreases
between 95 °C and 135 °C, most likely as a result of adsorbed mois-
ture loss. It is also possible that slow volatilisation of PEI may also
be occurring at these temperatures. Above 135 °C a more rapid de-
crease in mass occurs, especially in the presence of air where the
weight decrease is as a result of volatilisation and/or thermal deg-
radation. The volatility of PEI is reduced due to adsorption of the
polymer onto the silica surface [21] (see Supplementary mate-
rial). In the presence of CO2 there is a significantly increase in mass
as a result of the sorption of CO2 which is constant up to approxi-
mately 85 °C. The performance of the adsorbents is suited to CO2
capture after a flue gas desulphurisation (FGD) plant, maintaining
a high CO2 adsorption capacity at 60–75 °C (Fig. 2), close to the
temperatures at which flue gases are emitted [5]. Above 85 °C
CO2 adsorption becomes less favourable and adsorption capacity
decreases to a minima at 135 °C. Whilst it would be expected that
the adsorbent would undergo a further weight loss as seen in N2
and air above 135 °C, an increase in weight is observed (Fig. 2). This
indicates that a further secondary reaction is taking place between
the amine and CO2. The composition of this secondary reaction
product, the formation of which is further evident from a colour
change in the adsorbent, will be explored further by post-test anal-
ysis (Section 3.3).
3.2. Thermal swing adsorption cycles
Thermal swing regeneration in an atmosphere of CO2 is an
attractive method for the regeneration of the adsorbent. The use
of a stream of CO2 as sweep gas will result in the generation of a
pure stream of the gas with no need for further gas separations.
Although it is evident that the heating of the adsorbent to above
130 °C in the presence of CO2 will lead to a secondary reaction
(Section 3.1), the rate of formation, its stability and effect on adsor-
bent lifetimes when short regeneration times and optimised regen-
eration temperatures are employed needs to be explored.
The influence of temperature on the cyclic sorption capacity is
presented in Fig. 3. Cyclic adsorption capacity is measured as a per-
centage of the original capacity of the adsorbent, determined
 T.C. Drage et al. / Microporous and Mesoporous Materials 116 (2008) 504–512 507

12

4
weight change (wt.%)

-4
CO2

-8 N2

Air
-12
20 40 60 80 100 120 140 160 180 200
Temperature (ºC)

Fig. 2. Mass versus time profiles for polyethylenimine adsorbents in a flow of 20 ml min1 CO2, N2 and air. Measured using a slow heating rate of 0.25 °C per min.

100.00
Cycle 1
Cyclic capacity (% of original sorption capacity)

90.00 Cycle 2
Difference between cycle 1 and 2
80.00

70.00

60.00

50.00

40.00

30.00

20.00

10.00

0.00
180 170 160 155 150 145 140 135 130 125 120 110
Temperature (ºC)

Fig. 3. Effect of regeneration temperature over two successive TSA cycles (1 min regeneration cycles) on the regeneration performance of silica impregnated with 40 wt.% PEI,
1800 MM. 100% CO2 adsorption capacity is 2.4 mmol g1 of adsorbent.

during the first adsorption cycle therefore, 100% corresponds to ated, the recovered capacity of the second regeneration cycle de-
adsorption of 2.4 mmol g1 of CO2. It is evident that increasing creases concomitantly with increasing regeneration temperature,
the regeneration temperature from 110 to 145 °C results in a stea- culminating at 180 °C with a greater than 10% loss in capacity be-
dy increase in cyclic adsorption capacity. Including and above tween the first and second regeneration cycle. This loss of cyclic
145 °C approximately 90% of the original sorption capacity is adsorption capacity is as a result of the secondary reaction occur-
recovered, giving a cyclic capacity of 2.1 mmol g1. This positive ring between CO2 and the amine functional groups observed dur-
correlation between the regeneration temperature and desorption ing thermal stability analysis (Fig. 2). The destructive effect of
of CO2 is as predicted from thermal stability analysis of the adsor- this secondary reaction on cyclic capacity can be further illustrated
bents using TGA (Fig. 2). In terms of scale up and deployment of by simulating a greater number of regeneration cycles, performed
adsorption on a large scale, the greater the cyclic adsorption capac- by increasing the length of the thermal regeneration cycle to
ity, the less solid that is required in the system and potentially 60 min, assuming that the reaction rate is fastest at peak regener-
more efficient the process will be. Therefore, regeneration at ation temperature. Depending on regeneration temperature, a
145 °C would appear to be the optimum operating condition. How- decrease of up to 37 wt.% of initial capacity at 140 °C is observed
ever, it is evident that the cyclic adsorption capacity decreases for regeneration studied under CO2 for the PEI 1800 based adsor-
from the first to the second regeneration cycle for all temperatures bent (Table 1). In contrast the adsorbent can be seen to lose little
studied (Fig. 3). This is most pronounced above 145 °C, whilst of its original adsorption capacity when 60 regeneration cycles
approximately 90% of the original adsorption capacity is regener- are simulated in nitrogen (Table 1) eliminating the possibility that
508 T.C. Drage et al. / Microporous and Mesoporous Materials 116 (2008) 504–512

Table 1 is evident that regeneration at such high temperature has a detri-

Influence of PEI molecular mass (MM) on cyclic adsorption capacity determined by mental effect on the capacity of the unreacted adsorbent, with
regeneration for 60 min in CO2, air and N2
degradation of the polymer or loss of textural properties resulting
Regeneration temperature Cyclic adsorption capacity (% of original capacity) in a reduction in adsorption capacity in all cases. For this reason
(°C) TSA does not offer a feasible process for the cyclic use of PEI based
140 135 130
Regeneration gas CO2 Air N2 CO2 Air N2 CO2 Air N2
adsorbents. One possible route to allow for the use of TSA is to use
PEI 423 MM 61 70 90 56 77 92 62 86 94 adsorbent materials with a lower CO2 sorption enthalpy, therefore
PEI 600 MM 61 73 100 66 84 100 68 91 100 requiring lower regeneration temperatures to avoid secondary
PEI 1800 MM 67 89 98 63 92 99 69 96 100 reactions. For example, the use of adsorbents composed of pre-
dominantly secondary amine groups can lead to the need for de-
creased regeneration temperatures [22,23].
volatilisation of the polymer and loss of reactive amine groups is
responsible for the decrease in sorption capacity. Furthermore 3.3. Post-test analysis – Identification of the secondary reaction
the lesser extent of decrease in cyclic adsorption capacity in air product
shows that oxidative reactions may influence, but are not the main
cause of the loss of adsorption capacity. Prolonged exposure of PEI Identification of the secondary reaction product resulting from
600 MM and 1800 MM to a stream of CO2 (200 ml min1) at 140 °C the reaction of PEI with CO2 above 130 °C (Fig. 2) is important to
for up to 16 h, results in a 90% loss of adsorption capacity (see sup- fully understand the chemistry of CO2 sorption using solid sor-
plementary material). This clearly demonstrates the deleterious ef- bents. To investigate the nature of the secondary reaction the
fect on performance of adsorbent as a result of the secondary adsorbent was analysed in three forms, prior to contact with CO2,
reaction between CO2 and PEI over numerous regeneration cycles. after adsorbing CO2 at 75 °C, ‘‘at equilibrium” and after the ‘‘sec-
The influence of polymer molecular weight on regeneration sta- ondary reaction” with CO2, formed by heating PEI 1800 in CO2 at
bility has also been determined by the analysis, under identical 140 °C for 16 h resulting in a material almost exclusively composed
conditions, of the 600 MM and linear 423 MM forms of PEI (Table of the secondary reaction product. Analysis of the adsorbents in so-
1). It is apparent that the low molecular weight linear analogue, PEI lid state was required due to the insoluble nature of the organic
423, has the poorest lifetime performance of three types of PEI component of the adsorbent after the secondary reaction with CO2.
studied. Significantly over the range of temperatures studied PEI As a result of post-test analysis the reaction between CO2 and
423 MM is seen to lose adsorption capacity in nitrogen, whilst PEI above 130 °C is proposed to result in the formation of a urea
the higher molecular weight analogues do not. Therefore, it can linkage between two amine groups and the loss of water. Whether
be considered that the decreased recovered adsorption potential the reaction occurs from secondary reaction of the carbamate ion
in nitrogen is as a result of the loss of CO2 adsorbing amine func- formed on adsorption of CO2 (Reaction (3)) or direct reaction of
tional groups due to the volatilisation of the low molecular weight CO2 and the amine groups of PEI (Reaction (4)) cannot be deter-
polymer. Similarly a decrease in the performance of the polymer in mined from the results of this study (where R can be either H or
both CO2 and air can be attributed to its higher volatility. However, another PEI monomer).
it must be noted that whilst the weight loss of PEI 600 in N2 is neg-
ligible as for PEI 1800 at 140 °C, the stability of PEI 600 is signifi- R2 NHþ2 þ R2 NCOO $ R2 NCONR2 þ H2 O ð3Þ
cantly less that that of PEI 1800 in both air and CO2. This 2R2 NH þ CO2 $ R2 NCONR2 þ H2 O ð4Þ
suggests that there is some difference between the stability of
the polymer when reacting in CO2. These results indicate that the What is clearly evident from the results presented (Fig. 3) is that
high molecular mass, PEI 1800 MM, analogue of the polymer has the rate of formation of the urea linkage occurs at a slower rate
the best lifetime performance, as a combination of both the volatil- than the formation of the reversible carbamate ions (Reactions
ity and thermal stability of the polymer. (1) and (2)). The formation of dialkyl urea and possible reaction
Whilst the most efficient cyclic adsorption capacities are mechanisms has previously been reported from the direct reaction
achieved when TSA cycles are performed with regeneration above of amines and CO2 by a number of routes [24]. The following sec-
120 °C, the secondary reaction between CO2 and the amine groups tion describes how this assignment is consistent with the range of
destroys the adsorbents cyclic capacity, and therefore its useful chemical analysis of the adsorbent and also explains the physical
lifetime. The urea linkage can be regenerated to some degree in properties of the adsorbent after the secondary reaction. The most
N2, especially when heated for 1 h at 240 °C, where the adsorp- conclusive evidence for this assignment is from XPS analysis.
tion capacity increases from 0.5 mmol g1 to approximately Interpretation of the XPS spectra of the secondary reaction
1.0 mmol g1 (Table 2 and Supplementary material). However, it product identified three distinct components within the solid
material, the inorganic support, polyethylenimine and the urea
linkage (Table 3 and Supplementary material). XPS analysis was
Table 2 only performed on the secondary reaction product as analysis of
Adsorption capacities before and after high temperature regeneration of the PEI prior the equilibrium adsorbed CO2 or the original adsorbent as this
to contact with CO2 and after reaction of CO2 at 140 °C for 16 h would have resulted in the loss of polymer and/or CO2 in the high
Regeneration conditions Adsorption capacity vacuums employed during analysis. The inorganic support is evi-
dent from the assignment of the abundant Si 2p and O 1s in the
Prior to contact with After secondary
CO2 (mmol g1) reaction (mmol g1)
broad sweep analysis. The Si 2p and O 1s binding energies of
103.9 eV and 532.0 eV respectively are characteristic binding ener-
Temperature (°C) Time (min) Before After Before After
gies at SiO2 (Table 3) [25]. The next major component identified is
240 1 2.5 2.2 0.5 0.5 PEI, C 1s and N 1s binding energies at 400.0 eV and 258.4 eV
5 2.5 2.1 0.5 0.6
respectively closely match those of PEI reported in the literature
60 2.5 1.5 0.5 1.0
[26] and correspond to the parts of the polymer unaltered by reac-
250 1 2.5 2.1 0.5 0.7 tion with CO2. The remaining unidentified components C 1s, N 1s
5 2.5 1.9 0.5 0.8 and O 1s at 287.9 eV, 400.4 eV and 530.3 eV, respectively, present
60 2.3 1.2 0.5 0.9
in low concentrations, are attributed to the secondary reaction
 T.C. Drage et al. / Microporous and Mesoporous Materials 116 (2008) 504–512 509

Table 3
XPS binding energies and assignments

Element Binding energy Intensity Assignment Structure Reference

(eV) (mol%)
Si 103.9 20 SiO2 – inorganic support SiO2 [25]
O 532.0 29 SiO2 – inorganic support. Good agreement between the ratio of Si and O2 SiO2 [25]
O
530.8 1.5 Close match to urea/poly urea [26]
C
N N
O
C 287.9 5.3 Carbonyl carbon from urea fragment [26]
N N

285.4 30.2 Matches carbon skeleton of polyethylenimine C [26]

C N
O
N 400.4 1.8 Good match to nitrogen adjacent to a carbonyl group – such as poly urea [26]
R
N N
400.0 10.5 Close to nitrogen of polyethylenimine C [26]
C N
Assignment corresponds to the element in bold in the structures.

Table 4
Elemental composition and relative atomic ratio of the adsorbents (40% PEI loading) with CO2 adsorbed by carbamate ion formation at 75 °C (equilibrium) and after reaction of
CO2 and PEI at 140 °C for 16 h (secondary reaction product)

Adsorbent Elemental composition (wt.%) Atomic ratio

C H N O Total C/N H/N O/N C/O
PEI (measured) 21.5 4.7 12.7 0.0 39.0 2.0 5.2 0.0 –
PEI (calculated) 22.3 4.7 13.0 0.0 40.0 2.0 5.0 0.0 –
PEI, equilibrium adsorbed CO2 (measured) 23.5 4.2 10.5 7.3 45.5 2.3 4.8 0.5 4.3
PEI, equilibrium adsorbed CO2 (calculated) 22.5 4.6 11.7 6.7 45.5 2.3 5.5 0.5 4.5
PEI secondary reaction product 23.7 4.3 12.3 4.2 44.6 2.2 4.9 0.3 7.2

Calculated values determined from molar quantities with or without the addition of CO2 as determined from the TGA analysis.

with CO2 and PEI amine groups at elevated temperatures. Assign-
ment of these shifts led to the initial tentative assignment to be
made of urea type linkage present. All three of the binding energies
(Table 3) are in close agreement with the assignment of urea and
poly urea compounds reported in the literature [26]. Overall the
relative mol% for each of these components agrees with the assign-
ment. The formation of such compounds, effectively crosslinking
the PEI polymer also explains the loss of solubility of PEI, as well
as the strong binding of CO2 into the adsorbent. Similar reactions
have been reported for the formation of poly urea compounds by
the reaction of NH3 and CO2 [27].
The assignment of the secondary reaction product is further
supported by elemental analysis (Table 4). The elemental composi-
tion of the adsorbent prior to contact with CO2 and with CO2 ad-
sorbed at 75 °C is as predicted by calculation (Table 4). The
elemental composition of the adsorbent after the high temperature
reaction with CO2 is consistent with the assignment of a urea type
linkage. Whilst the atomic ratio of C/N is similar to that calculated
for CO2 adsorbed at equilibrium, the O/N ratio is approximately
half of this, as would be expected for the urea linkage.
13
C NMR spectra for the adsorbent before and after contact with
CO2 are presented in Fig. 4. Spectra for the adsorbent prior to con-
tact with CO2 contains a range of aliphatic carbons between 39 and
58 ppm (relative to an internal standard of TKS) indicative of the
alkyl groups of polyethylenimine adjacent to a mix of primary
(40–43 ppm), secondary (50–53 ppm) and tertiary (54–60 ppm)
amine groups of the polymer and possible combinations thereof
(Fig. 4a) [28]. PEI is composed of a 1:2:1 ratio of 1, 2 and 3 amine
groups and therefore the highest intensity of the peaks occurring at
50–53 ppm is consistent with the predominant carbon composi-
tion being adjacent to secondary amine groups. The chemical shift
at 165 ppm in the spectra of the adsorbent contacted with CO2 at
75 °C is indicative of the presence of carbamate ions, close to the
literature value of 166 ppm (NHCOO) [28]. In the case of the equi-
librium adsorbed material the ratio of aliphatic to carbonyl carbon
is 8:1, consistent with the 4:1 amine to CO2 ratio calculated to re-
sult from adsorption of 2.4 mmol g1 of CO2 on a 40% loading of PEI
(Fig. 2). Loss of resolution of the distinct aliphatic chemical shifts
compared to the adsorbent prior to contact with CO2 and decrease
in the intensity of the alkyl groups adjacent to primary amines
(40 ppm) is again as would be expected from CO2 sorption by car-
bamate formation. The spectra for the secondary reaction product
is intermediate of the adsorbent prior to and after equilibrium
adsorption of CO2 (Fig. 4a and b, respectively). Whilst the resolu-
tion of the chemical shifts in the aliphatic region is not sufficient
to unequivocally identify the presence of the urea linkage, the
shifts present are consistent with the unaltered and urea linked ali-
phatic carbons proposed form the secondary reaction product.
Moreover, the resonance at 164 ppm close to that reported in the
literature for urea linkages of 165 ppm [28] again further supports
the assignment of the secondary reaction product.
Infra-red analysis (DRIFT) of the adsorbent was performed to
further determination of surface functional groups (Fig. 5). The
adsorbent before contact with CO2 contains the expected bands
associated with the presence of N–H and C–H bonding previously
reported [29], the inorganic support is evident from the bands at
1100 cm1 and 790 cm1 from asymmetric and symmetric stretch-
ing of silicon dioxide vibrations. Bands for NH and NH2 groups at
3390 cm1 and 1600 cm1 and weak bands for CH2 at 2930 cm1,
2820 cm1 and 1440 cm1 are present from PEI. Subtle differences
are evident for the adsorbent with equilibrium adsorbed CO2 from
the appearance of a broad band at 1000 cm1 (Fig. 5c) that matches
510 T.C. Drage et al. / Microporous and Mesoporous Materials 116 (2008) 504–512

250 200 150 100 50 0 -50

Chemical Shift (ppm)

Fig. 4. 13C NMR spectra for the adsorbent: (a) prior to contact with CO2, (b) with CO2 adsorbed by carbamate ion formation at 75 °C and (c) after reaction of CO2 and PEI at
140 °C for 16 h.

the asymmetric and symmetric vibrations of carboxylate anions of

the carbamate ions [28]. The appearance of a strong broad band at
1650 cm1 in the spectra of the secondary reacted product (Fig. 5d)
matches those of carbonyl groups bonded to solid amine species
[28] and is therefore further evidence for the assignment made
by XPS analysis for urea linkages present.
In conclusion formation of the urea linkage from the reaction of
CO2 with PEI is proposed to be the reaction resulting in the loss of
cyclic adsorption capacity. The reaction has previously been re-
ported for amines and CO2 [27] and evidence for the assignment
is clear from spectral analysis. Cross linking of PEI by the formation
of urea cross linkages will also account for the loss of solubility and
decreased volatility of the polymer.

3.4. Regeneration using nitrogen as a stripping gas

To avoid the problems associated with TSA cycles in CO2, pres-

Fig. 5. DRIFT spectra for the adsorbent: (a) silica prior to addition of PEI, (b) silica-
PEI prior to contact with CO2, (c) CO2 adsorbed by carbamate ion formation at 75 °C
and (d) after reaction of CO2 and PEI at 140 °C for 16 h.
sure swing adsorption (TPSA) has been explored using nitrogen as
a simulated stripping gas, to lower the partial pressure of CO2.
Desorption profiles using N2 as a stripping gas for the adsorbent
loaded with 40 wt.% PEI are presented for a range of temperatures
and flow rates, 50 ml min1 and 100 ml min1 (Fig. 6). The peak in
the CO2 concentration of the desorption profile during the first
500 s of regeneration reflects the initial change of gas to N2 and
the time required for the oven to reach the required desorption
temperature. Increasing desorption temperature from 120 °C to
140 °C results in an increased rate of CO2 desorption (Fig. 6) as
would be predicted from the TGA analysis (Fig. 2).
Regeneration of the adsorbents at 75 °C is a lengthy process
requiring a large ratio of N2 to CO2 (Table 5). The benefit of in-
creased regeneration temperature is demonstrated by the dramatic
reduction in the amount of nitrogen required to desorb the CO2,
 T.C. Drage et al. / Microporous and Mesoporous Materials 116 (2008) 504–512 511

20

15 140 °C 50 ml/min

120 °C 100 ml/min

130 °C 100 ml/min

2

10 140 °C 100 ml/min

0
0 500 1000 1500 2000 2500 3000 3500
time (s)

Fig. 6. Thermal pressure swing desorption profiles for the inorganic support loaded with 40 wt.% PEI over a range of temperatures and flow rates.

Table 5
the PEI polymer be the formation of a urea type linkage above
Moles of nitrogen required to desorb 100, 99, 90 and 80% of the adsorbed CO2 over a 135 °C. Attempts to regenerate the adsorbent at high temperature
range of temperatures and flow rates in a CO2 atmosphere failed, therefore the formation of the urea
Regeneration temperature Flow rate Regeneration (mol N2/mol CO2)
linkage essential leads to the irreversible degradation of the adsor-
(°C) (ml min1) bent. As a result thermal regeneration of the chemical adsorbent is
100% 99% 90% 80%
seen to be a trade off between efficient regeneration, optimal at
75 100 244 150 93 61 140 °C, and degradation of the adsorbent. It is clear that thermal
120 100 96 48 20 16
swing regeneration in a CO2 atmosphere is not a feasibly method
130 100 57 20 13 10
140 50 53 10 5 4 for the cycling of PEI based adsorbents.
100 51 14 10 8 The use of nitrogen stripping gas at elevated temperatures (e.g.
140 °C) has been used to demonstrate to regenerate the adsorbent
using small quantities of stripping gas. Although nitrogen was used
as a stripping gas in this example, and would not be used in real
approximately 50% when regeneration temperature is increased
application of the technology, the results demonstrate that there
from 120–140 °C (Table 5). It is also evident that complete regen-
is potential for the use of steam stripping as a means of regenera-
eration of the adsorbent is a lengthy process, with 100% compared
tion. Further research is required to determine the cyclic adsorp-
to 99% of adsorbed CO2 removal requiring, for example a five fold
tion capacities of PEI based adsorbents.
increase on the moles of nitrogen stripping gas at 140 °C and
Whilst this work has involved exclusively the regeneration of
50 ml min1 (Table 5). The best conditions for regeneration of the
PEI based adsorbent, it is probable that similar reaction will occur
PEI based adsorbent required approximately five times as much
above 120 °C for other amine based adsorbent materials. Therefore
N2 to desorb 90% of the adsorbed CO2 (mol/mol) at 140 °C. Reduc-
regeneration strategies will need to be carefully selected to avoid
ing the flow rate of nitrogen at 140 °C, whilst increasing the overall
the irreversible degradation of adsorption performance as a result
time required for desorption (Fig. 6) results in a decrease in the
of urea linkage formation.
moles of nitrogen required to desorb 80–99% of the absorbed CO2
(Table 5).
Acknowledgments
Although nitrogen would not be used to regenerate adsorbents,
the efficiency of the pressure swing method induced by using
The authors thank The Carbon Trust (2002-6-38-1-1) for finan-
nitrogen as a stripping gas suggests that steam stripping is a viable
cial support. TD would like to thank the EPSRC (Advanced Research
technique for regeneration. Especially as the technique potentially
Fellowship EP/C543201/1) for funding. The authors would also like
overcomes the problems identified for the thermal regeneration of
to thank the reviewers for their constructive comments.
the adsorbents in a CO2 atmosphere. Using water vapour as a strip-
ping gas is an ideal technique in that the two gases can easily be
separated by condensation of the water phase. Future work will Appendix A. Supplementary data
simulate steam stripping as a technique for the regeneration of
PEI based adsorbents. Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.micromeso.2008.05.009.
4. Conclusions

Study of the cyclic performance of a PEI based adsorbent using References

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