M.Tech.

Dissertation Presentation - Simarjot Kaur 1

September 6, 2019
 M.Tech. Dissertation Evaluation

Carbon adsorbents synthesized from plastic waste for

CO2 capture

Simarjot Kaur
(Registration No: 601611004)

Under the guidance of

Dr. Haripada Bhunia Dr. Raj Kumar Gupta

Professor & Head Professor
Department of Chemical Engineering
Thapar Institute of Engineering &
Technology (Deemed to be University),
Patiala – 147004, Punjab
September 6, 2019 M.Tech. Dissertation Presentation - Simarjot Kaur 2
 Introduction

• Atmospheric CO2 concentration level has reached a value of ~410 ppm in 2018
from a pre-industrial value of ~280 ppm i.e. an increase of ca. 45% and it is
expected to reach up to 570 ppm by 2100.
• Uncontrollable increase in CO2 levels is because of strong dependence on fossil
fuels for meeting the energy requirements.
• Further this excess fossil fuel burning is depleting our environment by raising the
global temperature, sea level, melting of glaciers and surface ice.
• Probable solutions for this problem can be:
– developing efficient technologies so that demand for energy can be reduced and hence
reducing CO2 emissions,
– decreasing carbon intensity by switching to less carbon-intensive fuels or by using
renewable energy sources and/or nuclear energy, and
– carbon dioxide capture and sequestration (CCS) system.

September 6, 2019 M.Tech. Dissertation Presentation - Simarjot Kaur 3

 Introduction (contd.)
• Among these CCS is considered to be a key technology to drastically reduce
increasing CO2 concentrations in the near term and it acts as a bridging
strategy in providing time for the advancement of fossil fuel alternatives
along with decrease in overall CO2 mitigation cost.

• Adsorption is considered a
promising technology but
effective adsorbents need to be
developed.

• Post-combustion capture has the utmost potential in mitigating CO2 emissions

in the near term as it can be retrofitted to existing power plants which
contribute to two-thirds of CO2 generation.
September 6, 2019 M.Tech. Dissertation Presentation - Simarjot Kaur 4
 Literature review
Conventional adsorbents are found to exhibit low selectivity and poor
performance.

Extensive work has been carried out on amine modified adsorbents for CO2
capture. But impregnation of amines or high thermal treatments with various
chemical agents is sometimes considered less favourable as this leads to
blocking of pores of the adsorbent.

Many efforts have been made to fabricate materials, especially carbon based
adsorbents, with well developed pore structure and enhanced selectivity
towards CO2. They can be prepared from variety of raw materials and their
porous structure can be tailored based on the application.
September 6, 2019 M.Tech. Dissertation Presentation - Simarjot Kaur 5
 Research gap
It was observed that CO2 capture studies on synthesized carbons were
generally evaluated under static flow conditions at room temperature or 0 °C
which is not pertinent to flue gas application.

The present work focuses on the development of carbon based adsorbents

from plastic wastes using chemical activation technique.

Dynamic flow conditions for adsorption were considered in current studies.

September 6, 2019 M.Tech. Dissertation Presentation - Simarjot Kaur 6

 Objectives

Synthesis of carbon adsorbents from Poly(ethylene terephthalate) (PET)

waste.
Characterization of synthesized adsorbents for their relevant properties.
Study the adsorption performance of adsorbent using a fixed bed adsorption
setup operated at variable flow rates, temperatures, and feed concentrations
of CO2.
To fit the equilibrium and kinetic models for the experimental data.
To model the fixed bed adsorption process in order to predict breakthrough
curves.

September 6, 2019 M.Tech. Dissertation Presentation - Simarjot Kaur 7

 Schematic of the overall dissertation work
Synthesis of adsorbents
from plastic waste

Carbonization N2

Mixing KOH

Activation N2

Carbon
adsorbent
Textural properties N2 adsorption

Characterization
Chemical properties XPS
Performance
evaluation
Parametric study:
Temperature, CO2
concentration Dynamic adsorption
Capacity, Selectivity, measurements Modeling and
Regenerability (binary component) Simulation

Kinetic study Isotherm study

- Pseudo-first order - Langmuir

- Pseudo-second order - Freundlich
- Fractional order - Temkin

September 6, 2019 M.Tech. Dissertation Presentation - Simarjot Kaur 8

 Experimental section
Materials
S. No. Materials Source Characteristics

1. Plastic waste Household cold drink bottle waste

2. KOH M/s S. D. Fine Chemicals Ltd., India 100% pure

3. Sulfuric acid M/s S. D. Fine Chemicals Ltd., India 100% pure

4. Acetone M/s S. D. Fine Chemicals Ltd., India 100% pure

5. He gas Sigma Gases and Services, India 99.995% pure

6. N2 gas Sigma Gases and Services, India 99.995% pure

7. CO2 gas Sigma Gases and Services, India 99.999% pure

September 6, 2019 M.Tech. Dissertation Presentation - Simarjot Kaur 9

 Characterization of adsorbents

Characterization Equipment Conditions

Degassing at 220 °C under vacuum for 6

BET surface area and ASAP 2010, h;
pore volume Micromeritics, USA Nitrogen adsorption at liquid N2
temperature (-196 °C)
X-ray photoelectron Kratos AXIS ULTRA Emission current = 10 mA and anode
spectroscopy (XPS) DLD potential = 15 kV
Pressure < 2*10-9 torr
Low resolution scan pass energy = 50 eV
High resolution scan pass energy = 20 eV

September 6, 2019 M.Tech. Dissertation Presentation - Simarjot Kaur 10

 Fixed-bed adsorption study setup

I.D. = 9.39 mm
Height = 300 mm

Schematic diagram of adsorption study setup

• Adsorption
– Adsorbent amount: 2 g
– Temperature: 30 °C, 50 °C, 75 °C 100 °C
– Condition: 5-12.5% by volume of CO2
– Total feed rate: 80 ml min-1
• Desorption
– Temperature: 200 °C
– Condition: 100% by volume of N2
September 6, 2019
• Adsorption–desorption cycle was repeated 4 times to check the cyclic stability of the adsorbents. 11
M.Tech. Dissertation Presentation - Simarjot Kaur
 Modeling & Simulation of Fixed Bed Adsorption
Mass balance on fixed adsorber unit can be applied in form:
+1 +2 1. Convective mass transfer
2. Axial dispersion
3. Mass of adsorbate adsorbed
by adsorbent
4. Accumulation of adsorbate
3-
4
C b
(1+)-(1-) u
x
 2 Cb
(2+)-(2-)  Dax
1- 2- x
1   b qt
(3-)  b t
C b
(4)
t
September 6, 2019 M.Tech. Dissertation Presentation - Simarjot Kaur 12
Modeling & Simulation of Fixed Bed Adsorption (cont.)
Overall mass conservation balance equation for the bulk gas in the bed

Cb ( x, t )  (uCb ( x, t )) Cb ( x, t ) 1   b qt ( x, t )

Dax    0
x 2
x t b t
where
Cb is Gas concentration in the bulk flow
u is Interstitial velocity in bed
Ɛb is Bed porosity
Dax is the Axial dispersion coefficient

September 6, 2019 M.Tech. Dissertation Presentation - Simarjot Kaur 13

 Modeling & Simulation of Fixed Bed Adsorption (cont.)

Concerning the diffusion within particle, Linear driving force model (LDF)
which provides an adequate approximation using a simple form was
considered
LDF (linear driving force model) equation:

q p 3k f
s  Cb  Cs 
t ap
where kf (m s-1) is film mass transfer coefficient and Cb (mol m-3) is bulk
phase concentration ,and Cs (mol m-3) concentration at equilibrium.

September 6, 2019 M.Tech. Dissertation Presentation - Simarjot Kaur 14

 Results and Discussion
Adsorbent synthesis

Carbonization Carbon adsorbent

Heating rate = 10 ºC min-1
PET waste Temperature = 700 ºC (Reference sample)
Holding time = 2h

Activation of samples
Mixing Drying
Carbon Temperature = 500-800 ˚C
(KOH: PET = 1-
adsorbents (105 ºC, 12 h) Heating rate = 10 ºC min-1
4:1)
Holding time = 2h

Carbon
adsorbent

September 6, 2019 M.Tech. Dissertation Presentation - Simarjot Kaur 15

 BET surface area

N2 adsorption and desorption isotherms at -196 °C

• Isotherms of prepared adsorbents can be classified as Type IV isotherm, indicating

the presence of micropore and mesopores.
• The volume of N2 adsorbed for the sample which is directly carbonized is very low,
signifying less pores and it is highest for the sample activated using PET:KOH mass
ratio 3 indicating sample having well developed porous structure.
• The samples indicate H4 hysteresis loop, which is a characteristic of mesoporous
materials.
September 6, 2019 M.Tech. Dissertation Presentation - Simarjot Kaur 16
 BET surface area (contd.)
Textural properties of nitrogen enriched porous carbon
Materials Surface area (m2 g-1) Pore volume (cm3 g-1)

PET-700 9.86 0.009

PET-1-700 481.51 0.24
PET-2-700 951.29 0.30
PET-3-700 1,478.28 0.47
PET-4-700 943.89 0.41

With the increase of KOH:PET activation mass ratio till 3, BET surface area and
pore volume increases from 481.51 to 1478.28 m2 g-1 and 0.24 to 0.47 cm3 g-1
respectively, but further increase resulting in decrease in surface area and pore
volume.
When the KOH:PET mass ratio was 4 some pores collapsed, due to over
activation by partially cracking micropores.
The sample PET-700 shows negligible surface area signifying non-porous nature.

September 6, 2019 M.Tech. Dissertation Presentation - Simarjot Kaur 17

 X-ray photoelectron spectroscopy (XPS)
O1s high resolution spectra of PET-700 and PET-3-700

Relative content (%)

Peak Position Assignment
PET-700 PET-3-700
O1 530.34 Carboxylate group - 18.69
O2 531.05 Carbonyl group 32.30 31.3
O3 531.85 Hydroxyl group 7.61 27.2
O4 532.8 Carboxylic group 60.11 20.7
September 6, 2019 M.Tech. Dissertation Presentation - Simarjot Kaur 18
 Dynamic CO2 adsorption-desorption study
CO2 adsorption
Sample capacity (mmol
g-1)
PET-1-700 0.65

PET-2-700 1.01

PET-3-700 1.3

PET-4-700 0.88

PET-700 0.54

(a) Breakthrough curves of carbon adsorbents with 12.5% CO2 at 30 °C, and (b) equilibrium
adsorption capacity of prepared adsorbents at 30 °C under 12.5% CO2 (c) CO2 uptake capacity of
different adsorbents
- Mainly carboxylic groups present - Mainly carbonyl group followed by carboxylate
followed by carbonyl and group
carboxylate - These groups exhibit basicity thereby providing
active sites for acidic CO2 adsorption
 Increase in capacity of PET-3-700 due to development of abundant micro pores
and increase in basic functional
September 6, 2019
groups.
M.Tech. Dissertation Presentation - Simarjot Kaur 19
 Dynamic CO2 adsorption-desorption study (contd.)

(a) Selectivity of PET-3-700 at 12.5% CO2 and 30 °C , (b) Breakthrough curves for PET-3-700 of fresh and adsorbent after
multiple regeneration and (c) adsorption-desorption cycle for PET-3-700 under 12.5% flow at different
temperatures
N2 is observed immediately in the outlet depicting less adsorption capacity for N2 while CO2
was not detected for around 2 minutes depicting higher affinity towards CO2
(C/C0>1) shows N2 occupies more sites initially but with time N2 is swapped by CO2
depicting higher selectivity of adsorbents towards CO2
Adsorption capacity is observed to be practically constant over four cycles, showing
complete regeneration of PET-3-700
September 6, 2019 M.Tech. Dissertation Presentation - Simarjot Kaur 20
 Kinetics study
Kinetic Parameter Temperature (°C)
Model 30 50 75 100

Fraction kn
0.75 0.27 0.53 0.06
al order
(mmol1-m gm-1 min-n)
qe
1.25 1.05 0.76 0.57
(mmol g-1)
n
6.25 3.33 1.56 4.68
m
9.67 4.36 1.18 0.91
R2
CO2 uptake kinetics: Experimental and 0.98 0.93 0.91 0.98
model predicted capacities at 12.5% CO2 Error%
at 30 °C and 1.09 1.65 0.96 0.94

 Fractional order kinetic model generated best fit with the experimental data with R2 value
of 0.98 and least Error% value.

September 6, 2019 M.Tech. Dissertation Presentation - Simarjot Kaur 21

 Isotherm study
Model Parameter Temperature (°C)
30 50 75 100

Freundlich KF 11.09 7.14 6.23 3.24

(mmol g-1
atm-1/n)
n 1.96 1.04 1.00 1.16

R2 0.98 0.96 0.97 0.98

CO2 uptake isotherm on PET-3-700:

Experimental and model predicted values

Based on coefficient of determination (R2), the best result for the equilibrium data
fit with the Freundlich isotherm at different adsorption temperatures.
This shows that the surface is heterogeneous .
Value of n more than 1 indicates favorable adsorption condition.

September 6, 2019 M.Tech. Dissertation Presentation - Simarjot Kaur 22

 Simulation of adsorption process

Experimental results v/s simulated breakthrough plot

LDF model for mass transport in adsorption process was considered and simulated
model using MATLAB software predicted good result for concentration profile inside
the bed at CO2 concentration of 12.5% and adsorption temperature of 30 °C.
 Justifying the theoretical scenarios by validating the mass balance and parameters
values predicted using different set of equations.
September 6, 2019 M.Tech. Dissertation Presentation - Simarjot Kaur 23
 Conclusions
 Surface area and CO2 adsorption capacity of the synthesized carbon adsorbents increased
with KOH activation.
 The surface area and total pore volume of the synthesized adsorbent prepared at 700 ˚C
along with KOH:PET mass ratio of 3 have been found to be maximum of 1428.78 m2 g-1 and
0.47 cm3 g-1, respectively.
Dynamic CO2 adsorption capacity of PET-3-700 has been 1.3 mmol g-1 at 30 °C.
 Synthesized and activated carbon adsorbent showed complete regenerability, stability and
better selectivity for CO2 over N2.
 Fractional order kinetic model has been found to best describe the CO2 adsorption on
prepared carbons over the entire adsorption region.
 Adsorbent surface was heterogeneous in nature dominated with physiosorption behavior
confirmed from Freundlich model fitting.
 The fixed bed adsorption simulation showed good match with the experimental data
obtained for breakthrough studies.

September 6, 2019 M.Tech. Dissertation Presentation - Simarjot Kaur 24

 Publications
Under preparation
 Balpreet Kaur, Simarjot Kaur, Raj Kumar Gupta and Haripada
Bhunia, “CO2 adsorption studies on activated carbons developed
from PET waste: Experimental & Theoretical analysis” (Preparing)
Other publications:
 Deepak Tiwari, Simarjot Kaur, Haripada Bhunia, and Pramod K.
Bajpai, “CO2 adsorption on oxygen enriched nanostructured carbons
derived from silica templated resorcinol-formaldehyde”, Journal of
Industrial and Engineering Chemistry, 2018. Manuscript ID: JIEC
3964 S1226-086X(18)30196-5 (Impact Factor: 4.841)

September 6, 2019 M.Tech. Dissertation Presentation - Simarjot Kaur 25

 Acknowledgements
My M.tech supervisors – Dr. Haripada Bhunia, Professor & Head and
Dr. Raj Kumar Gupta, Professor at Department of Chemical
Engineering, Thapar Institute of Engineering & Technology (Deemed
to be University), Patiala.
Dr. Raj Kumar Arya, Associate Professor & P.G. coordinator,
Department of Chemical Engineering, Thapar Institute of Engineering
and Technology.
Mr. Deepak Tiwari for his guidance and Motivation.
All the faculty members, staff members, colleagues at Department of
Chemical Engineering, Thapar Institute of Engineering & Technology.

September 6, 2019 M.Tech. Dissertation Presentation - Simarjot Kaur 26

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September 6, 2019 M.Tech. Dissertation Presentation - Simarjot Kaur 27

 Thanks

September 6, 2019 M.Tech. Dissertation Presentation - Simarjot Kaur 28