Rajshahi University of

Engineering and Technology

Department of Chemical and Food Process
Engineering

literature Review
on
Thesis and Project

Submitted By:
Safat Anam (1511001)
Mazharul Ahmed (1511016)
Title: Effect of moisture on Nano-Silica Adsorbent.
Introduction:

The CO2, from the emission of industrial flue gases is one of the burning issue at present. Emission of
CO2 contributes to climate change and raising global temperature. We tried to find out a way to
capture this CO2 from flue gases. There are some existing technology to capture CO 2 like - Absorption
& stripping which is very expensive. Some emerging technology include Adsorption, Cryogenic
separation, Oxy-combustion etc. In future Adsorption will be a possible economic capturing system.
Literature Review:
There are different advanced separation methods that are used during combustion process for the separation
of CO2 from flue gas (Leung et al., 2014; Ahmed et al., 2020). These methods are Absorption, Adsorption,
Membrane Separation and Cryogenics (Lee et al., 2013; Pires et al., 2011; Samanta et al., 2012; Ahmed et al.,
2020). Post-combustion capture-based technology is considered widely for carbon dioxide capture from flue
gases (Karka, Kodukula, Nandury & Pal, 2019). The most matured technology to separate CO2 from flue gas is
absorption based (Karka, Kodukula, Nandury & Pal, 2019). Despite the high efficiency of absorption, this
method has major drawbacks including corrosion of mechanical parts, release of toxic chemicals and gases,
and requirement of high energy for regeneration, has limit the application of this technology (Parshetti et al.,
2015; Tian et al., 2018). Adsorption is more efficient alternative method for CO2 capturing and could replace
amine-based absorption technique (Babu et al., 2017). In adsorption, CO2 is selectively captured on the
surface of adsorbent by different mechanisms such as chemical adsorption (chemisorption) or physical
adsorption (physisorption) (Bhown and Freeman, 2011; Ahmed et al., 2020). Adsorption has three different
regeneration process: i.e. (i) TSA, (ii)PSA and (iii)VSA (Ahmed et al., 2020). This literature focusses only on PSA.
To use the PSA process for the removal and recovery of CO2 from hot fuel gas streams at high temperatures,
the first and most important issue is to find an appropriate adsorbent. Such an adsorbent must have (i) high
selectivity and adsorption capacity for CO2 at high temperatures; (ii) adequate adsorption/ desorption kinetics
for CO2 under operating conditions; (iii) a stable adsorption capacity towards CO2 after repeated
sorption/desorption cycles; and (iv) adequate mechanical strength of adsorbent particles after cyclic exposure
to high-pressure streams (Dave et al. 1999; Hufton et al. 1997; Zou & Rodrigues, 2001). Adsorption process
requires a good adsorbent, regeneration process and adsorption cycle time to carry out efficient removal of
adsorbate from the system. There are plenty of materials that have been studied for CO2 adsorption such as
metal-organic frameworks (MOF), porous carbons, zeolites, etc. These adsorbents are cost effective,
environment-friendly, having high surface area and resistant to water and chemicals (Ben-Mansour et al.,
2016; Zhao et al., 2018). Carbon-based adsorbents exhibit an adequate adsorption capacity towards CO2 at
low pressures and ambient temperature. However, the adsorption capacity is reduced with increasing
adsorption temperature (Zou & Rodrigues, 2001). Zeolites are very important adsorbents for CO2 gas
separation and purification (Kyaw et al. 1997; Yang 1987; Ruthven 1997; Ustinov and Klyuev 1999; Rouf and Eic
1998; Huesca et al, 1999; Suzuki et al. 1997; Ghosal et al. 1999; Khelifa et al. 1999; Zou & Rodrigues, 2001)
because CO2 has a high linear quadrupole moment which interacts with intra-zeolite cations (Khelifa et al.
1999; Zou & Rodrigues, 2001). Zeolite has been investigated mostly and especially zeolite 13X, which has been
regarded as a benchmark material for CO2 capture because of its high CO2 adsorption capacity (Karka,
Kodukula, Nandury & Pal, 2019). In comparing, the performance of CO2 PSA with two adsorbents, zeolite 13X
gives more favorable results than activated carbon (Chue, Kim, Yoo, Cho & Yang, 1995). It had the largest pore
diameters and the largest Na/Si ratios (Siriwardane, Shen, Fisher & Losch, 2005). In spite of this feature, zeolite
is found to be more effective at ambient temperature as physical adsorption is more predominant in these
materials and less effective at higher temperatures. To make zeolite operational at higher temperatures and
near atmospheric pressures (real flue gas conditions), suitable amine-modified/ impregnated zeolite is
prepared and tested for their capacity in various study, as these prepared materials would act as a hybrid
adsorbent, wherein both physisorption and chemisorption would take place. The studies on amine-modified
adsorbents have earned significant attention in CO2 capture research area because of its simple chemistry
involved between the acidic CO2 molecule and basic amine molecule impregnated on the solid surface (Karka,
Kodukula, Nandury & Pal, 2019). (Chen et al., 2015) modified 13X zeolite by using a mesopore-generating
agent and then with PEI800MW. It is found that the mesoporous 13X zeolite showed better CO2 capture
capacity and selectivity at high temperature (e.g., 100 °C) with dilute CO2 concentrations. Recently, diverse
amines have been used in the synthesis of amine−zeolite adsorbents, including Monoethanolamine (MEA),
Tetraethylenepentamine, Polyethylenimines (PEIs), and so forth (Karka, Kodukula, Nandury & Pal, 2019). In
recent research, PEI has drawn great attention in CO2 capture study using different supports because of its
easily synthesizable property, relatively less cost and lastly because of its high thermal stability when
compared with other amines (Shen et al. 2017). PEI is two types: (i) Branch and (ii) Linear. Li et al. has
considered the influence of the PEI type and molecular weight on the CO2 capture performance. It was
observed that the CO2 adsorption capacity diminished with the increasing PEI molecular weight, and branched
PEIs had higher sorption capacities than linear PEIs because of their greater mobility (Karka, Kodukula,
Nandury & Pal, 2019). It was also found that branched PEI of 800 molecular weight with the silica support
showed highest CO2 sorption capacity of 202 mg of CO2/g of the adsorbent at 105 °C under pure CO2
atmosphere (Li et al. 2014). however, LPEIs were more stable than BPEIs during CO2 sorption–desorption
cycling. It is found that the 60 wt % PEI-modified 13X zeolite showed betterment in CO2 adsorption capacity
at 75°C over unmodified zeolite 13X by a factor of 2.3 at 75 °C with fast kinetics with a maximum co2
adsorption capacity of 1.22 mmol/g in pure atmospheric co2 (Karka, Kodukula, Nandury & Pal, 2019). It was
found that Avrami’s fractional order and dual kinetic models (DKM) described well the adsorption behaviour of
CO2 on PEI-impregnated zeolite 13X at all temperatures accurately and up to 75 °C (Karka, Kodukula, Nandury
& Pal, 2019). Remarkable adsorption enhancements were observed when the adsorbents were exposed to a
SH of 3.8– 11.5 mg H2O/g at 25°. Increasing further the SH 11.5 mg H2O/g or above had no additional benefit
for linear PEI and even decreased the CO2 uptake for branched PEI. Above 55°C the difference in adsorption
capacity under dry and humid conditions was minimal mainly due to much lower amounts of water being
adsorbed at higher temperature Increasing the loading of PEI in the adsorbent resulted in an increase in water
adsorption (Zhang, Goeppert, Olah & Prakash, 2017). It was observed that the CO2 uptake of the sorbent
increased in the presence of moisture by a maximum of 9 mol% under flue gas containing 7.7% moisture in
comparison to the adsorption under dry conditions. The presence of moisture increased the heat of
regeneration of the sorbent significantly. It was calculated that the energy demand increased approximately
two-fold on introduction of 14.7% moisture compared to that of dry flue gas (Sandhu, Pudasainee, Sarkar &
Gupta, 2016).

The main aim of this research project is to make a adsorbent bed with Nano-Silica and combination with PEI
and observed the effect of moisture on the co2 adsorption and compare the result with the unmodified zeolite
13x, and dry condition of flue gas.

Materials Required:
 BPEIs (MW: 800) (Li, Jiang, Yan, Tian & Chen, 2014)
 Nano silica (precipitated silica, Sipernat 306; surface area: 336 m2/g, density: 0.36 g/ml, primary particle size: 7
nm) (Li, Jiang, Yan, Tian & Chen, 2014)

 Methanol (HPLC grade) (Li, Jiang, Yan, Tian & Chen, 2014)

 CO2 (99.999%) (Li, Jiang, Yan, Tian & Chen, 2014)

Methodology:
The desired amount of PEI was dissolved in 25 mL of methanol and stirred for 30 min at room temperature,
then, 2 g of nano silica and another 5 mL of methanol were added. Subsequently, the solution was stirred for 5
h at room temperature. The products were then dried in an oven at 50°C for 2 h, and dried again in an oven
under vacuum (<1 mm Hg) at 50°C for 2 h. To determine the actual PEI loading content, we need to determine
the carbon (C), hydrogen (H), and nitrogen(N) contents of the products using elemental analysis (Li, Jiang, Yan,
Tian & Chen, 2014).
References:
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598. doi: 10.1021/ie00041a020
2. Zou, Y., & Rodrigues, A. (2001). Adsorbent Materials for Carbon Dioxide. Adsorption Science & Technology, 19(3),
255-266. doi: 10.1260/0263617011494141
3. Siriwardane, R., Shen, M., Fisher, E., & Losch, J. (2005). Adsorption of CO2on Zeolites at Moderate
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10.1016/j.apenergy.2014.09.057
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