Development of new granulated nanoporous materials for application of CO 2

capture and regeneration by PSA Technology

(might add the CO2 process introduction if still too short)

Material:

Carbon dioxide capture and storage IPCC (2005) (1)

https://www.mdpi.com/1996-1073/15/3/887 (2)

CO2 adsorption by swing technologies and challenges on industrialization - ScienceDirect (3)

CO2 Sorption - ScienceDirect (4)

Catalysts | Free Full-Text | Metal-Organic Frameworks as a Platform for CO2 Capture and Chemical
Processes: Adsorption, Membrane Separation, Catalytic-Conversion, and Electrochemical Reduction of
CO2 (mdpi.com) (5)

CO2 capture using N-containing nanoporous activated carbon obtained from argan fruit shells -
ScienceDirect6

Sci-Hub | Activated carbons from biomass-based sources for CO2 capture applications |
10.1016/j.chemosphere.2021.131111 (3800808.com)7

Sci-Hub | Adsorption of volatile organic compounds by metal-organic frameworks MOF-177. Journal

of Environmental Chemical Engineering, 1(4), 713–718 | 10.1016/j.jece.2013.07.005 (3800808.com)8

Sci-Hub | Regeneration, degradation, and toxicity effect of MOFs: Opportunities and challenges |
10.1016/j.envres.2019.05.019 (3800808.com) 9

COP26: Vietnam's Commitment to Reducing Emissions (vietnam-briefing.com)

1.1 CO2 Emission is a Global problem

As technology advances, humanity encounters an increasing array of

challenges, one of which is the greenhouse gas emission. Greenhouse gas
(GHG) are gases in Earth's atmosphere that trap heat, thus contributing to the
greenhouse effect. This effect is a natural process necessary for maintaining a
habitable temperature on our planet. But human has significantly increased the
concentration of these gases leading to an enhanced greenhouse effect and
global warming. Common greenhouse gases include carbon dioxide (CO2),
methane (CH4), nitrous oxide (N2O), and fluorinated gases.

Figure 1.1: Global greenhouse gas emission statistic by the IPCC

CO2 takes up the largest percentage of the total greenhouse gas emission more
specifically CO2 from fossil fuel and industrial processes.
2022*
-----------------------
37.49
 Figure 1.2: Annual CO2 emissions worldwide from 1940 to 2022
(in billion metric tons)

In the figure 1.2, since the third industrial revolution in the 1950s, the growth
of CO2 emission has drastically increased. In the year 1950, the CO 2 emission
reached around 5 billion tons this value has increased by multiple of 5 after 50
years. In 2022 the emission nearly doubled the amount emitted in the year 2000
with the staggering number of 37.49 billion tons.

Carbon dioxide (CO2), one of the primary greenhouse gases responsible for the
enhanced greenhouse effect, excessive CO2 in the atmosphere leads to global
warming and climate change which have significant negative impact on
environment as well the human race.

1.2 Possible Solutions: (2)

There are There are four different ways to reduce CO2 emission levels:

1. Reducing the use of fossil fuels by:

+improving the efficiency of energy conversion processes

+using renewable (non-fossil fuel) energy sources

+increasing the use of green hydrogen

2. Replace technologies using fossil fuels with a low carbon to hydrogen

C/H2 ratio by replacing coal and oil with gaseous fuels.

3. Capturing CO2 from fuel combustion in power plants and other industrial
processes and storing it in appropriate geological structures, in exhausted or
exploited gas or crude oil deposits

4. Limiting deforestation processes and thus storing more CO2 in biomass

With all the solutions from above, we still have to consider that a large portion
of the energy we use is generated via fossil fuel so switching energy source is
no the viable option. Since most of the CO 2 emission came from fossil fuel, the
most effective approach should be reducing the amount of CO 2 being emitted
from the industrial processes by using the carbon capture and storage (CCS)
method.

1.3 CO2 capture introduction (1)

The propose of CO2 capture is the produce a vessel containing concentrated

amount of CO2 that can be transported to the storage site. The reason
concentrated CO2 is preferred because of it would be more efficiency for space,
cost.

CO2 is typically removed to purify other industrial gas streams. But most of the
cases the CO2 is then emitted to the atmosphere. Only a few plants actually
store the captured CO2 for commercial proposes.

Depending on the process and application of the plants, there are three main
approaches to capture the CO2: pre-combustion, post-combustion and oxyfuel.
However, due to the complexity and diversity of industrial processes, there
may be variations or adaptations to these approaches to achieve better cost-
efficiency, performance and environmental impact.
 Figure 1.3: Overview of CO2 capture processes and systems.

In addition to the three main branches of approach, there are also other
branches of techniques that can be used:

Figure 1.4: Methods and Techniques for CO2 capturing (2)

Due to the unique attributes of Physical adsorption such as high selectivity,

non-reactive, require low energy to operate, simple conditions, cost effective
works both for post-combustion and pre-combustion which can be retrofitted in
almost any plants without much modification. We have decide to research
further into this technology.

There are many types of physical adsorption:

Nowadays, activated carbon (AC) is known as the most popular material which
can be used in CO2 capture techniques and methods. The advantages of AC
materials are the avaibility of AC and low cost. AC also can be produced by
low-cost biomass or waste precursors ( friendly with environment ). AC shows
the stable reaction when it works under the moist environment due to their
hydrophobic, and they can be regenerated by thermal or evacuation with lower
energy demand. However, commercial AC are usually produced by coal, peat
or petroleum coke and these resources can not be renewable so that it can affect
to the production of AC. With the expensive reactivation process and high
regenerations of these solid materials which that can be difficult in producing a
large amount of AC for human’s demand.In the results after carring out a CO2
capture process with AC, there exist other organic components, temperature,
pH and the arrangement of design also affect to the efficiency of adsorption
process.The load factor fluctuates between 10-30%[5]. The results in reality is
lower than theory 1-5%[5].This means human need a large cost in operation
and maintenance .AC can be regenerated in industry with thermal method but
in this method’s process, the stage could be up to 800 or 900 degree Celcius[5].
To advoid the oxidation of AC, the process could be carried out in vaccum or
inert atmosphere so that it require an additional energy for heating and results
in high investment and operation costs.

The other meterial is MOFs, the main limitation of this material is the high
cost. The synthesis process of MOFs costs an expensive price, which made
them can not access to the commercial. The process in synthesis MOFs is easy
to design. Comparing the MOFs to other absorbents like AC, zeolite and so on,
MOFs have an easy optimization of the structure pores, surface functions and
properties, it make them become more specific and precise application in pores
materials in CO2 capture. MOFs are devided into two classes: rigid and
dynamic/flexible. Flexible MOFs hold a dynamic and soft framework in a fast
reaction with the environment, such as, temperature, pressure and guest
molecules. In the other hand, rigid MOFs show a stable and strong porous
framework with an enduring porosity is similar to zeolites [5].MOFs is not
stable in high temperature (up more than 500) and low temperature in vacuum.
MOFs’ coordination linker can be broken in acid or base evironment. Because
of the toxicity of MOFs, so that the regeneration of these materials get some
problem.[8]

Zeolites are also widely use for the CO2 capture in physical adsorption
technology, particularly in post-combustion carbon capture. Compared to other
materials, zeolites have relatively high stability, working capacity and low
material and processing cost. Besides that, there are drawbacks such as most
zeolites produced in powder form while large-scale industrial processes prefer
granulated form, high humidity effect due to their hydrophilicity which reduces
the capture efficiency.
 Figure 1.5: Pros and cons comparation of selected carbon-capture adsorbents
[5]

Introduction about physical absorption methods : VSA, TSA and PSA

Temperature swing adsorption (also known as TSA) is the first adsorption
method which was used in industry. In TSA, we cost more time in regeneration
than PSA but the results of purity of CO2 is high ( more than 95%) and recover
more than 80% of CO2 in the adsorbents [3]. For example about the energy-
consuming of TSA, when we use TSA methods with zeolites, it will cost more
energy than chemical adsorption like amine adsorption method. On top of that,
the drawback of TSA in time-consuming causes from the slow rate in heating
and cooling so that it limits the time of circulation [4].

Vacuum swing adsorption (VSA) is a modification of PSA methods with the

reduction of energy-consumption, easy-access operating procedure. The
different between VSA and PSA is the low absolute pressures and the affinity
affects to absorbents [4].

The last one and the methods we will use in our project to regenerate the
absorbents is pressure swing adsoption (PSA). The apply of PSA in absorption
is seperating the gas mixture such as CO2 in amonia production. PSA is
attracted to the researchers due to its simple operation, high performance at
every-condition temperature. PSA can separate the gas at the low temperatures
and high pressure, just by put a reactor through the absorbents. The machenism
of PSA in high presure, CO2 is adsorbed on the surface of solid adsorbents,
then swinging the pressure down, at amospheric pressure, take the CO2 from
the absorbents and transport. This method is popular in commercial because of
its effectiveness (up to 84%) and it is applied in almost electrical plants [3] .

1.4 Introduction to zeolite (3)

Zeolites have their potential for CO2 capture owing to their high porosity,
ultra-small pores, structural diversity, high stability, and excellent recyclability
and chemical reactivity which are the reasons why it is selected for this
research

COP 26 in Viet Nam

Conference of the Parties (COP) was a session which was established in 1994
in United Nations Framework Convention of Climate Change (UNFCCC).
COP26 was hosted by UK and Italia from October 31 st to November 12th in
2021, in Glasgow.