You are on page 1of 121

Thesis on

STUDIES ON PURIFICATION OF NATURAL GAS


USING CRYOGENIC TECHNOLOGY
Submitted by

BISWAJIT DEBNATH
Class Roll no: 001310302012
Examination Roll No: M4CHE1508
Registration No: 124707 of 2013-14
Session: 2013-2015

Master of Chemical Engineering


Project Supervisor

Prof. (Dr.) Kajari Kargupta


This project report is submitted towards the completion of
Master of Engineering degree in Chemical Engineering

DEPARTMENT OF CHEMICAL ENGINEERING


JADAVPUR UNIVERSITY
KOLKATA 700 032

Faculty of Engineering & Technology


Department of Chemical Engineering
Jadavpur University
Kolkata 700032
DECLARATION OF ORIGINALITY
I, Sri Biswajit Debnath, declare that this thesis is my own work and
has not been submitted in any form for another degree at any
university or other institute of tertiary education. Information derived
from the published and unpublished work of others has been
acknowledged in the text and a list of references is given in this
thesis.
I also declare that I have pursued the Master of Chemical Engineering
course in accordance with the requirements of the universitys
regulation, Research practice and ethical policies have been complied
with appropriately
Name: Biswajit Debnath
Exam Roll No: M4CHE1508
Class Roll Number: 00131302012
Thesis Title: Studies on Purification of Natural Gas Using Cryogenic
Technology.

Signed: ___________________

Date: ___________

Faculty of Engineering & Technology


Department of Chemical Engineering
Jadavpur University
Kolkata 700032

CERTIFICATE
This is to certify that Mr. Biswajit Debnath, a final year student of
Master of Chemical Engineering Examination student of Chemical
Engineering

department,

Jadavpur

University

(Class

Roll

No:

001310302012; Examination Roll No: M4CHE1508; Registration No:


124707 of 2013-14), has completed the thesis work titled Studies on
Purification of Natural Gas Using Cryogenic Technology under the
supervision of Prof. (Dr.) Kajari Kargupta during his Masters
Curriculum. This work has not been reported earlier anywhere and can be
approved for submission in partial fulfillment of the course work.

________________________
Prof. (Dr.) Kajari Kargupta
Thesis Supervisor
Department of Chemical Engineering
Jadavpur University

Prof. (Dr.) Chandan Ghua


Head of the department
Department of Chemical Engineering
Jadavpur University

Dean
Faculty of Engineering and Technology
Jadavpur University

Faculty of Engineering & Technology


Department of Chemical Engineering
Jadavpur University
Kolkata 700032
CERTIFICATE OF APPROVAL
The foregoing thesis, entitled as Studies on Purification of Natural Gas
Using Cryogenic Technology is hereby approved by the committee of
final examination for evaluation of thesis as a creditable study of an
engineering subject carried out and presented by Mr. Biswajit Debnath
(Class Roll No: 001310302012; Examination Roll No: M4CHE1508;
Registration No: 124707 of 2013-14) in a manner satisfactory to warrant
its acceptance as a perquisite to the degree of Master of Automobile
Engineering. It is understood that by this approval, the undersigned do not
necessarily endorse or approve any statement made, opinion expressed or
conclusion drawn therein, but approve the thesis only for the purpose for
which it is submitted.

Committee of final examination for evaluation of thesis

To my family, my friends and


my inspirations (Late Suptish C. Nandy,
Late Jim Morrison and Late B.B. King)

CONTENTS
List of Figures

List of Tables

viii

Nomenclature

ix

Acknowledgement

ABSTRACT

CHAPTER 1: INTRODUCTION

4-23

1.0 Energy Demand


1.1 Natural Gas
1.2 Existing Carbon Capture and Storage Technologies
1.2.1 Chemical Looping
1.2.2 Absorption
1.2.3 Adsorption
1.2.4 Membrane Technology
1.2.4 Cryogenic Technology
1.3 Research Methodology

CHAPTER 2: LITERATURE REVIEW

24-39

2.0 Historical Background


2.1 Detailed Literature Review
2.1.1 Thermodynamics and Solidification
2.1.2 Conventional Cryogenic Technology
2.1.3 Non-conventional Cryogenic Technology
2.1.4 Hybrid Technology
2.2 Research Gap
2.3 Objectives

CHAPTER 3: MODEL DESCRIPTION

40 52

3.0 Problem Statement


3.1 Nucleation Theory
3.2 Description of packed bed setup
3.3 Experimental Procedure

3.4 Transport Phenomena Model for CO2 Separation on Single Packing


3.4.1 Mass-transfer and kinetics of nucleation
3.4.2 Energy-Balance Equation
3.4.3 Thermodynamic, mass and heat transfer correlations used for simulation
3.5 Transport phenomena model for CO2 capture using cryogenically cooled packed
bed with multiple Packing
3.5.1 Modeling of Desublimation of Carbon dioxide inside the
Capture/Deposition Zone of the Packed Column
3.6 Solution Technique

CHAPTER 4: RESULTS & DISCUSSION

53 85

4.0 Desublimation kinetics of Carbon dioxide on a single packing from gas stream
4.1 Results of simulation with pure carbon dioxide feed gas stream
4.1.1 Variation of frost layer thickness () with time at different inlet gas flowrate
4.1.2 Rate of frost layer deposition with time at different inlet gas flowrate
4.1.3 Rate of change of frost layer thickness with time at different inlet gas
flowrate
4.1.4 Variation of Interface Temperature with time at different inlet gas flowrate
4.2 Results of simulation with carbon dioxide and methane mixture as feed gas stream
4.2.1 Variation of frost layer thickness () with time at different bulk pressure
4.2.2 Rate of change of frost layer deposition with time at different inlet gas
flowrate
4.2.3 Variation of Particle Temperature with time at different bulk Pressure
4.2.4 Variation of Interface Temperature with time at different inlet gas flowrate
4.3 Effect variation of CO2 percentage on Frost Layer Thickness
4.4 Effect of CO2 composition on Particle Temperature
4.5 Dynamics of CO2 capture inside a cryogenically cooled packed bed with pure CO2
as feed
4.5.1 Variation of frost layer thickness with time at different position along the
bed for co current flow
4.5.2 Variation of frost layer thickness with time at different position along the
bed for counter current flow

ii

4.5.3 Contour plot of frost layer thickness with time and axial position for co
current flow
4.5.4 Contour plot of frost layer thickness with time and axial position for counter
current flow
4.5.5 Surface plot of frost layer thickness with time and axial position for counter
current flow
4.5.6 Growth of frost layer thickness with time and axial position for counter
current flow
4.5.7 Variation of outlet mass flowrate thickness with time and axial position for
counter current flow
4.5.8 Surface Plot of frost layer thickness with time and axial position for counter
current flow
4.5.9 Percentage separation of carbon dioxide of with axial position at different
time for counter current flow
4.5.10 Contour plot of percentage separation of carbon dioxide with time and
axial position for counter current flow
4.5.11 Contour plot of frost layer deposition on only packing surface
(heterogeneous nucleation) with time and axial position for counter current flow
4.5.11 Surface plot of frost layer deposition on only packing surface
(heterogeneous nucleation) with time and axial position for counter current flow
4.5.12 Contour plot of frost layer deposition on only bed wall (heterogeneous
nucleation) with time and axial position for counter current flow
4.5.13 Surface plot of frost layer deposition on only bed wall (heterogeneous
nucleation) with time and axial position for counter current flow
4.5.14 Effect of homogeneous nucleation on saturation time during the capture
cycle
4.5.15 Effect of inlet gas feed flowrate on bed saturation time during the capture
cycle

4.6 Dynamics of CO2 capture inside a cryogenically cooled packed bed with 80%
CO2 as feed
4.6.1 Variation of frost layer thickness with time at different position along the
bed for counter current flow

iii

4.6.2 Variation of normalized mass flow with axial distance at different time
for 80% CO2 composition in feed gas mixture and countercurrent flow
4.7 Validation of simulation results with experimental results

CHAPTER 5: CONCLUSION

86 87

5.0 Conclusion
5.1 Future Scope
References

98 101

Appendix I

102 104

Appendix II

105 106

iv

List of figures
Fig no

Description

Fig. 1

Demand of Natural Gas by Region projected to 2035.

Fig. 2

Reserves to Production (R/P) ratios of natural gas by regions

Fig.3

Natural Gas Consumption by sector, 2013

Fig. 4

Natural Gas Consumption by country, 2013

Fig. 5

Distribution of high CO2 gas fields by country.

Fig. 6

General Carbon Capture and Storage process.

Fig. 7

Post, Pre and Oxyfuel combustion processes.

Fig. 8

Process flow diagram of a typical amine-solvent (MDEA)-based chemical


absorptionsystem for the separation of CO2 and other acid gases from natural gas.

Fig. 9

Pressure Temperature Phase Diagram for CO2.

Fig. 10

Gibbs Free energy difference for homogeneous and heterogeneous nucleation

Fig. 11

The Packed Bed Experimental Setup

Fig. 12

Schematic diagram of a packed bed and a single packing with frost layer

Fig. 13

Schematic Diagram explaining the Algorithm

Fig. 14

Effect of inlet gas flow rate on carbon dioxide frost layer thickness ( )

Fig. 15

Effect of inlet gas flow rate on rate of deposition of carbon dioxide frost layer

Fig. 16

Effect of inlet gas flow rate on rate of change of carbon dioxide frost layer

Fig. 17

Effect of inlet gas flow rate on Interfacial Temperature (Ti)

Fig. 18

Effect of bulk pressure on frost layer thickness with time

Fig. 19

Effect of inlet gas flow rate on rate of deposition of frost layer thickness

Fig. 20

Effect of bulk pressure on Particle Temperature (Tp)

Fig. 21

Effect of inlet gas flow rate on Interfacial Temperature (Ti)

Fig. 22

Effect of variation of carbon dioxide in feed gas stream on frost layer thickness

Fig. 23

Effect of variation of carbon dioxide in feed gas stream on Particle Temperature


(Tp)

Fig. 24

Growth of CO2 frost with time at different axial position of the bed for
Co current flow at 5 lpm inlet gas flowrate and Temperature Profile 3

Fig. 25

Growth of CO2 frost with time at different axial position of the bed for
Counter current flow at 5 lpm inlet gas flowrate and Temperature Profile

Fig. 26

Contour plot of CO2 frost vs. time vs. Axial position for

Co current flow at 5 lpm inlet gas flowrate and Temperature Profile 3


Fig. 27

Contour plot of CO2 frost vs. time vs. Axial position for Counter current flow at 5
lpm inlet gas flowrate and Temperature Profile 1

Fig. 28

Contour plot of CO2 frost vs. time vs. Axial position for Counter current flow at
10 lpm inlet gas flowrate and Temperature Profile 3

Fig. 29

Surface plot of CO2 frost vs. time vs. Axial position for Counter current flow at
5 lpm inlet gas flowrate and Temperature Profile 3

Fig. 30

Growth of CO2 frost with time at different axial position of the for Counter
current flow at 10 lpm inlet gas flowrate and Temperature Profile 3

Fig. 31

Variation of outlet Mass flowrate with time at different axial position of the for
Counter current flow at 10 lpm inlet gas flowrate and Temperature Profile 3

Fig. 32

Surface plot of outlet mass flowrate vs. time vs. Axial position for Counter
current flow at 10 lpm inlet gas flowrate and Temperature Profile 2

Fig. 33

Percentage separation of CO2 frost vs.

Axial position at different time for

Counter current flow at 5 lpm feed flowrate and Temperature Profile 3


Fig. 34

Contour plot of percentage separation of CO2 vs. time vs. Axial position for
Counter current flow at 5 lpm inlet gas flowrate and Temperature Profile 3

Fig. 35

Contour plot of deposition of CO2 frost on packing vs. time vs. Axial position
for Counter current flow at 5 lpm inlet gas flowrate and Temperature Profile 3

Fig. 36

Surface plot of deposition of CO2 frost on packing vs. time vs. Axial position for
Counter current flow at 5 lpm inlet gas flowrate and Temperature Profile 3

Fig. 37

Contour plot of deposition of CO2 frost on bed wall vs. time vs. Axial position
for Counter current flow at 5 lpm inlet gas flowrate and Temperature Profile 3

Fig. 38

Surface plot of deposition of CO2 frost on bed wall vs. time vs. Axial position
for Counter current flow at 5 lpm inlet gas flowrate and Temperature Profile 3

Fig. 39

Effect of Homogeneous Nucleation on the saturation time for the capture cycle
for Counter current flow at 5 lpm inlet gas flowrate and Temperature Profile 3

Fig. 40

Effect of inlet gas feed flowrate on the saturation time for the capture cycle for
Counter current flow at 5 lpm inlet gas flowrate and Temperature Profile 3

Fig. 41

Growth of CO2 frost with time at different axial position of the bed for Counter
current flow at 5 lpm inlet feed gas flowrate and Temperature Profile 3

Fig. 42

Variation of normalized mass flow with axial distance at different time for
Counter current flow at 5 lpm inlet gas flowrate and Temperature Profile 3

vi

Fig. 43

Comparison of simulation and experimental results of variation of percentage


CO2 with time at different bed temperature profiles for Counter current flow at 5
lpm gas flowrate

vii

List of tables
Table no.

Description

Typical Composition of natural Gas

U.S. pipeline composition specifications for natural gas delivery

PVTX experimental data for carbon dioxide mixtures

viii

NOMENCLATURE
Symbol

Property
mass of CO2 frost deposited on the packing
mass transfer co-efficient in the CO2 stream side
bulk pressure in the flue gas
saturation pressure of CO2 at the interface

time

convective heat transfer co-efficient


latent heat of desublimation for CO2

temperature within the frost layer


radial distance from the surface of the packing
density of the glass packing
specific heat of the packing material
thermal conductivity of the CO2 frost

frost layer thickness

Sh

Sherwood number

Nu

Nusselts number

Re

Reynolds number

Pr

Prandtls number

Sc

Schmidts number
Density of CO2 frost
Total number of packing particle in a single layer
Mass of CO2 flowing into the column
Mass of CO2 flowing out of the column

Volumetric flow rate of CO2 in

CO2

Density of CO2 in gas phase

ix

Mass of N2 flowing out of the column


Density of nitrogen gas in the column
Mass fraction of CO2 in exit stream of single layer
mg

Mass flow rate of the CO2 stream

Cg

Specific heat capacity of CO2 gas

Tg

Temperature of the flowing CO2 stream

Ap

Cross-sectional area of the packed column

Packing density

Acknowledgement
It would be a great pleasure for me to take the opportunity to humbly express my gratitude for
the innumerable gestures of help, cooperation and encouragement which I have received from
my teachers, friends and all of my well wishers during this course. First of all, I would like to
express my immense gratitude to the Chemical Engineering Department of Jadavpur University
for assigning me the project entitled Studies on Purification of Natural Gas using Cryogenic
Technology.

I am deeply indebted to my Project Supervisor Prof. (Dr.) Kajari Kargupta, for


providing me with an opportunity to work on this interesting field which has a great impact on
making a clean environment upon successful exploitation. Her insight and expertise in the field
of modeling and simulation have enriched me more than anything else. Also I would like to take
this opportunity to acknowledge that her guidance not only helped to complete my project but
also showed me new light in my life. She has been always there even when I pretended to
understand everything and anything but I didnt. Her commitment, dedication and undisputed
love towards me have helped me to grow both as a human being as well as in the field of
chemical engineering.

I am very grateful to Prof. (Dr.) Chandan Guha, Head of the Department, Chemical
Engineering Department and all other faculty members for their help and cooperation. I want to
thank all the teachers and staff of the Chemical Engineering Department.

I would like to extend my thanks to our lab mates who have supported me. My sincere
appreciation also extends to all my colleagues and others who have provided assistance at
various occasions.

I would also like to thank Ms. Shubhanwita Saha, Mrs. Punam

Mukhopadhyay, Mr. Rahul Baidya, Mr. Rayan Kundu, Ms. Upasana Das and Ms. Aryama
Raychaudhuri for their help in peer reviewing the thesis and help with the English. I would also
like to extend my gratitude towards Ms. Ditipriya Hazra, Ms. Sanghamitra Das, Mr. Riju De and
Mr. Shambojit Roy for their help in downloading research papers which I were unable to access.

I would also like to acknowledge Ms. Eapsita Pahari, Ms. Suchismita Paul, Mrs.
Moumita Sardar, Ms. Shimanti Chandra and my specially good friend MON for their help and
mental support when I was struggling to figure out things regarding this project.

And last but not least I would like thank Lokenath Baba, Jim Morrison (JimDa), Lucile
II, Mr. Bapi Debnath my father, Mrs. Rekha Debnath my mother, Mr. Swarup Mondal my meso,
Ms. Sayantani Mondal my sister and my maternal grandparents for their love, blessings, faith in
me and all other kinds of support during the period of my Masters Degree.

Biswajit Debnath
P.G. Student
Department of Chemical Engineering
Jadavpur University

ABSTRACT
The growing concern of low carbon foot print and energy demand it is now necessary to invade
the impure gas wells and proper technology for methane enrichment. In this study cryogenic
separation of carbon dioxide has been carried out in the solid vapour zone, from pure carbon
dioxide and carbon dioxide gas mixtures. A two step model has been considered the mass
transfer from bulk gas to the packing and the nucleation of carbon dioxide frost on the packing.
These two resistances are considered to be in parallel. A single packing was considered for
transport phenomena modeling and there after it was embedded into a multiple packing model.
Simulations were carried out to study the spacio- temporal evolution of frost layer thickness both
in single packing and multiple packing. The effects of bulk pressure and composition of carbon
dioxide on frost layer thickness, rate of change of frost layer thickness, rate of frost deposition,
interfacial temperature and partial temperature were simulated. The results showed that higher
carbon dioxide concentration results in higher frost layer thickness. Simulations were also
carried out for the total bed. Contour and 3D surface plots of frost layer thickness and mass flow
rate reveals that effective separation depends on inlet pressure flow rate, temperature profile and
flow configuration. They also affect the frost deposition. It was also found that counter current
flow configuration with respect to liquid nitrogen ensures better separation than co-current flow
configuration. The significance of the study is in design and optimization of cryogenic separation
of carbon dioxide from flue gas and natural gas.

This Page is left


Intentionally Blank

CHAPTER
1
INTRODUCTION

1.0 Energy Demand


The appetite for oil, natural gas, and other energy sources is growing dramatically, with
worldwide energy consumption projected to increase by more than 40 percent by 2035. The
growing demand is fueled by a population that is predicted to increase 25 percent in the next 20
years, with most of that growth in countries with emerging economies, such as China and India.
This phase of very high energy consumption growth is driven by the industrialization and
electrification of non-OECD economies, notably China. The 2002-2012 decade recorded the
largest ever growth of energy consumption in volume terms over any ten year period. There is a
clear long-run shift in energy growth from the OECD to the non-OECD. Virtually all (95%) of
the projected growth is in the non-OECD, with energy consumption growing at 2.3% p.a. OECD
energy consumption, by contrast, grows at just 0.2% p.a. over the whole period and is expected
to fall from 2030 onwards. By sector, industry will always remain the dominant source of growth
for primary energy consumption, both directly and indirectly (in the form of electricity). Industry
accounts for more than half of the growth of energy consumption. Although it is forecasted that
the growth in renewable (6.4% p.a.) is going to be the fastest amongst all the fuels but in the final
decade (considering a projection till 2035) gas is the largest single contributor to growth that
being the fastest growing among fossil fuels (1.9% p.a.) and the only one to grow more rapidly
than total energy. Rising energy demand from economic output and improved standards of living
will likely put added pressure on energy supplies. For example, in China alone, demand is
expected to increase by 75 percent by 2035. Simultaneously worldwide consumption of
petroleum and other liquid fuels raised from 87 MMbbl/d in 2010 to 98 MMbbl/d in 2020 and
projected to rise to 119 MMbbl/d in 2040. The growth in other liquid supplies is attributed to byproducts of natural gas production (in the case of NGPL) and government policies aimed at
increasing the use of alternative liquid fuels in the transportation sector. Other liquid supplies
account for between 14% and 17% of total liquid fuel supplies throughout the projection period
of 2040. Energy demand will grow, especially in the non-OECD (Organization for Economic
Co-operation and Development) countries, which accounts for much of the uncertainty about
future demand growth.
Global demand for natural gas is projected to grow by 1.9% p.a., reaching 497 Bcf/d by
2035, with non-OECD growth (2.7% p.a.) outpacing the OECD (1% p.a.). Global gas supply is
expected to grow to 172 Bcf/d by 2035. Shale gas is the fastest growing source of supply (6.5%

Fig. 1: Demand of Natural Gas by Region projected to 2035


(B.P. Energy Outlook 2035)
p.a.), providing nearly half of the growth in global gas. On the demand side, shale gas gives US
natural gas a competitive advantage relative to other fuels. This is already visible in the power
sector, where gas is likely to continue to grow (0.5% p.a.) at the expense of coal, despite the
rapid expansion of renewables. Next, gas is expected to gain market share in the industrial sector,
from 39% in 2012 to 42% by 2035. And finally, gas will start to penetrate the transport sector.
Gas is the fastest growing fuel (18% p.a.) in a sector where overall demand is falling (-0.9%
p.a.). By 2035 gas will account for 8% of US transport sector fuels, almost matching biofuels.

1.1 Natural Gas


Natural gas is used primarily as a fuel and as a raw material in manufacturing. It is used in
home furnaces, water heaters, and cooking stoves. As an industrial fuel, it is used in brick,
cement, and ceramic-tile kilns; in glass making; for generating steam in water boilers; and as a
clean heat source for sterilizing instruments and processing foods. As a raw material in
petrochemical manufacturing, natural gas is used to produce hydrogen, sulfur, carbon black, and
ammonia. Ethylene, an important petrochemical, is also produced from natural gas.

The discovery of natural gas dates from ancient times in the Middle East. Thousands of
years ago, it was noticed that natural gas seeps ignited by lightning created burning springs. In
Persia, Greece, or India, people built temples around these eternal flames for their religious
practices. However, the energy value of natural gas was not recognized until approximately 900
BC in China, and the Chinese drilled the first known natural gas well in 211 BC.
Natural gas exists in nature under pressure in rock reservoirs in the Earths crust, either in
conjunction with and dissolved in heavier hydrocarbons and water or by itself. It is produced
from the reservoir similarly to or in conjunction with crude oil. Natural gas has been formed by
the degradation of organic matter accumulated in the past millions of years. The principal
constituent of natural gas is methane. Other constituents are paraffinic hydrocarbons such as
ethane, propane, and the butanes. Many natural gases contain nitrogen as well as carbon dioxide
and hydrogen sulfide. Trace quantities of argon, hydrogen, and helium may also be present. The
composition of natural gas can vary widely. Table 1-1 outlines the typical makeup of natural gas
before it is refined.
Table 1: Typical Composition of natural Gas (Wikipedia)

Name

Formula

Volume (%)

Methane

CH4

70-90%

Ethane, Propane & Butane

C2H6, C3H8, C4H10

0-20%

Carbon Dioxide

CO2

0-8%

Oxygen

O2

0-0.2%

Nitrogen

N2

0-5%

Hydrogen sulphide

H2S

0-5%

Rare gases

A, He, Ne, Xe

trace

Natural gas can also contain a small proportion of C5+ hydrocarbons. When separated, this
fraction is a light gasoline. Some aromatics such as benzene, toluene, and xylenes can also be
present, raising safety issues due to their toxicity. Natural gas can contain other contaminants
too. Acid contaminants, such as mercaptans (R-SH), carbonyl sulfide (COS), Carbon dioxide
(CO2) and carbon disulfide (CS2) might be present in small quantities. Mercury can also be
present either as a metal in vapour phase or as an organo-metallic compound in liquid fractions.
Concentration levels are generally very small, but even at very small concentration levels,

mercury can be detrimental due its toxicity and its corrosive properties (reaction with aluminium
alloys).
According to ExxonMobil Energy Outlook Report 2015, global demand for natural gas is
projected to rise by 65 percent from 2010 to 2040, the largest volume growth of any energy
source. The extensive utilization of NG has led to decreased NG reserves to production ratio over
regions of the world, among which Middle East has the highest ratio as shown in Figure 2.

Fig. 2: Reserves to Production (R/P) ratios of natural gas by regions

Natural gas, also called the prince of hydrocarbons as it has many applications. The
proportion of the natural gas consumed for energy production in major fields including
industrial, commercial, residential, transportation and in generating electricity for the year 2009
is shown on Fig. 3.

Fig.3: Natural Gas Consumption by sector, 2013

Natural gas consumption is the highest in United States and Russia, followed by North America
and Middle East. Figure 4 shows the natural gas domestic consumption worldwide in 2013.

Fig.4: Natural Gas Consumption by country, 2013 (Enerdata.net)

10

Natural gas consists primarily of methane (70-90% of the total component) and other light and
heavier hydrocarbons. The impurities present in natural gas need to be removed to meet the
pipeline quality standard (NaturalGas.org 2010). The allowable amounts of common impurities
in U.S. for the delivery of the natural gas to the pipe line are given below.
As one of the major contaminates in natural gas feeds, carbon dioxide must optimally be
removed as it reduces the energy content of the gas and affect the selling price of the natural gas.
Moreover, it becomes acidic and corrosive in the presence of water that has a potential to
damage the pipeline and the equipment system. In addition, when the issue of transportation of
the natural gas to a very far distance is a concern, the use of pipelines will be too expensive so
that Liquefied Natural Gas (LNG), Gas to Liquid (GTL) and chemicals are considered to be an
alternative option. In LNG processing plant, while cooling the natural gas to a very low
temperature, the CO2 can be frozen and block pipeline systems and cause transportation
drawback. Hence, the presence of CO2 in natural gas remains one of the challenging gas
separation problems in process engineering for CO2/CH4 systems.
Table 2. U.S. pipeline composition specifications for natural gas delivery
(Al-Juaied 2004; Baker 2004)
Components

U.S. Pipeline Specification

Hydrocarbons (C3+)

950 1050 Btu/scf dew point -20OC

CO2

< 2 mol%

H2S

< 4 ppm

H2O

< 0.1 gm/m3 (<120 ppm)

Total inert (N2, He, Ar etc.)

< 4mol%

The ever growing energy demand has led to the re-evaluation of the development potential of
economically unviable, contaminated natural gas reserves [Fig. 5] at diverse regions of the Earth
like South China Sea, Gulf of Thailand, Central European Pannonian basin, Australian CooperEromanga basin, Colombian Putumayo basin, Ibleo platform, Sicily, Taranaki basin, New
Zealand and North Sea South Viking Grabenetc (Thrasher & Fleet, 1995).

11

Fig. 5: Distribution of high CO2 gas fields by country (Maqsood et al., 2014)
The chaos around the world with crude oil and due to increased demand on natural gas has
stimulated the researchers to develop, design and modify cryogenic technology for Natural Gas
separation. Presence of carbon dioxide (CO2) and other sour gases in varying quantities in
different natural gas resources has endorsed several innovative sequestrating technologies to be
invented to mitigate the anthropogenic CO2 emission as well as maintaining greenhouse gas level
in the atmosphere. And research is still going on.
Despite of the fact that several literatures is available on removal of sulfur containing
gases and higher hydrocarbons, now the focus must be shifted towards the removal of carbon
dioxide efficiently form gas stream. With growing economy and population driving the demand
of energy associated with lean and green slogans have made it imperative for the researchers to
innovate and materialize new technologies to deal with the natural gas reserves containing CO2
up to 80%. Natural gas is mostly considered as a "clean" fuel as compared to other fossil fuels,
the natural gas found in reservoirs deposit is not necessarily "clean" and free of impurities. One
third of the proven natural gas reserves are estimated to be sour. Malaysia alone constitutes more
than 13 Tscf of undeveloped natural gas because of the high CO2 concentration. In some gas
fields, the concentration of CO2 exceeds 70 percent (Darman & Harum, 2006). Therefore
separation of carbon dioxide is necessary to maintain the selling price of the natural gas with

12

quality because CO2 reduces the calorific value of the gas making it economically unfeasible.
The high content of CO2 in natural gas enhances the formation of carbonic acids and dry ice
causing corrosion and clogging of delivery pipelines. Hence, the removal of CO2 from the
natural gas is important for maintaining the quality of the product to satisfy the customer. Also,
purification of raw natural gas is necessary so as to not facilitate pipeline corrosion and to satisfy
the pipeline standards for different NG companies. Therefore, the impurities must be removed to
meet the pipe-line quality standard specifications as a consumer fuel, enhance the calorific value
of the natural gas, avoid pipelines and equipment corrosion and further overcome related process
bottle necks.

1.2 Existing Carbon Capture and Storage Technologies


Raw natural gas collected from the wells is often impure. Purification is carried out at different
stages to meet different pipeline specification, as standardized internationally & nationally. CO2
being one of the most notorious acid gases purification is important as to meet standards &
commercialization.

Fig. 6: General Carbon Capture and Storage process

13

Different existing technologies are there which are widely used for CO2 separation from natural
gas stream as well as flue gas streams which evolves in different processes in industries. Existing
technologies includes absorption, adsorption, cryogenic technology, membrane technology,
chemical looping etc. These technologies have been developed over the years in order to meet
environmental regulations, pipeline specifications and optimize the operational costing. Figure 6
represents a general Carbon Capture and Storage process.

Fig. 7: Post, Pre and Oxyfuel combustion processes


Oxyfuel Combustion is the process by which nearly pure oxygen fires power plants instead of
air, producing a flue gas stream comprising water and carbon dioxide. The water is condensed
which leaves the pure CO2 stream. Generally, there exists as Air Separation Unit (ASU) which is
built on the front end of Oxyfuel combustion power plants, which employs cryogenic technology
to distill out Oxygen from air. This process is very difficult & energy intensive. Since, firing is
carried out with pure Oxygen, it causes high flame temperature. As a result the boilers are
required to be rebuilt & circulation of flue gas is required to control heat flux & flame

14

temperature. An ASU and Oxyfuel combustion decrease plant electrical output by approximately
30% (Nielson 2012).
In post combustion carbon capture process, the CO2 is captured from the flue gas after fuel
combustion [Fig. 7]. While this process can be retrofitted to any existing process plant, dilute
CO2 concentration present on the flue gas at low pressure makes it energy intensive to capture as
a large volume of gases are required to be handled.
In the following section, different CCS technologies have been discussed in details.

1.2.1 Chemical Looping


Chemical looping is a process in which oxygen, typically from air, oxidizes a metal oxide
particle in an oxidizing reactor, releasing heat and is then transported to a reducing reactor where
it mixes with fuel & converts to a less oxidized state. In this case, generally two fluidized beds
are interconnected that allows the metal oxide particles to circulate between both reactors. Here
the metal oxide acts as an oxygen carrier, no other elements of air comes into contact with fuel
and doesnt mix up with CO2 produced from fuel oxidation. As a result, the flue gas stream
contains only water & CO2. The disadvantage is that metal oxides are expensive & deactivate
with time. Actually, the cycling temperatures of the metal oxides represent a significant amount
of entropy generation with the loss in Gibbs free energy associated with it (Nielson 2012).

1.2.2 Absorption
Absorption process is one of the most well known, established, industrially applicable state of
the art technologies in natural gas purification process where a component of a gaseous phase is
contacted with a liquid in which it is preferentially soluble. Most of the conventional CO2
removal processes from natural gas are based on either chemical or physical or simultaneous
physical-chemical absorption process. Absorption is usually carried out in a countercurrent tower
(column), through which liquid descends and gas ascends. The reverse process (which is also
termed as stripping process, desorption) is employed when it is required to remove the absorbed
gases from the solvent for the purpose of recovery of the gas or the solvent or both. The
efficiency of any sorbent to absorb CO2 or H2S is expressed by its loading capacity. The two
major cost intensive factors associated with the absorption process include: i) the solvent
circulation rate and loading capacity required to achieve the degree of sweetening and ii) the

15

high energy consumption regarding the regeneration of the solvent (Biruh Shimekit and Hilmi
Mukhtar 2012, Kidnay and Parrish, 2006, Mullick 2014).
Absorption process can be classified into two categories- a) physical absorption process
and b) chemical absorption process. In physical absorption process implemented for CO2
removal the major controlling parameters are temperature, pressure of the feed gas stream and
partial pressure of the acid gas components present in the feed gas stream. A condition of low
feed temperature and high partial pressure (10 bars or more) is favorable for commercialization
of the process physical solvents have weak affinity towards the acid gas components. Hence, it is
necessary to employ high solvent circulation rate and limited loading capacity. In this case, less
energy is required for the regeneration step compared to traditional amine based processes as it is
carried out in low pressure. However, if the carbon dioxide is to be utilized for Enhanced Oil
Recovery (EOR), the cost of compressing the gas increases energy requirement. This method can
be implemented where the feed stream is rich in carbon dioxide and the product purity doesnt
matter a lot (Yeo et al, 2012). Chemical absorption process, takes place as exothermic reaction
between the chemical sorbent and the target acid gas component (CO2) at low temperature.
During the process, strong chemical bonds are formed between the target component and the
functional group of the chemical sorbent. The percentage separation of acid gas component is
dependent on the loading capacity of the sorbent predetermined by the available active sites (Yeo
et al., 2012, Christopher et. al., 2008). In the chemical process industry two types of chemical
solvents are used 1) Aqueous amine solution and 2) Carbonate solution. Selective absorption of
acid gases by exothermic chemical reaction with amine groups is the key concept of this process
and it is widely applied in the natural gas industries. The common amine based solvents used for
the absorption process are monoethanolamine (MEA), diethanolamine (DEA) triethanolamine
(TEA), diisopropanolamine (DIPA), diglycolamine (DGA) and methyldiethanolamine (MDEA)
that reacts with the acid gas (CO2 and H2S) to form a complex or bond. The basicity is provided
by the amine function, and it provides reactivity to remove the acid gases. The hydroxyl groups
serve to increase the solubility of amine in water. This effect reduces the vapor pressure of the
amines so that less is lost out the top of the absorber or stripper (Glasscock 1990, Biruh
Shimekit and Hilmi Mukhtar 2012). The Sour gases are brought in contact with the amine
solution in a countercurrent flow through an absorption column allowing the sorbent to strip out
CO2 or H2S selectively from the NG. The sweetened gas comes out from the top of the column

16

where as the sorbent loaded with sour gas components exits from the bottom which is further
directed to another column for regeneration. The stripping or desorption is carried out at a higher
temperature (about 373 K 473 K) giving out a high concentrated pure CO2 stream after
dehydration. The regenerated solvent is cooled down and recycled to the top of the column.
Absoprtion is well known for being the easiest and most common method for acid gas removal
from natural gas; but high solvent regeneration cost, equipment corrosion by acid compounds,
low loading capacity, amine degradation by SOx, NOx, HCl, HF, and O2 in flue gas, high solvent
circulation rate etc are some of the barrier towards the wide application in real field. (Liu et. al.,
2009; Olajire, 2010).

Fig. 8: Process flow diagram of a typical amine-solvent (MDEA)-based chemical absorption system
for the separation of CO2 and other acid gases from natural gas (Hubbard, 2010; Kohl and Nielsen,
1997)

CO2 removal from sour gas stream at a high pressure and temperature by using hot alkali
carbonate solutions like potassium carbonate (K2CO3) or sodium carbonate (NaCO3) was first
implemented in 1950s (Kohl and Nielsen, 1997). The process was first commercialized by US
Bureau of Mines as Benfield Process in 1954. Since the rate of absorption of CO2 by carbonate
solution increases with rise in temperature, the process is carried out at a high temperature 383 K
389 K. In cryogenic process units, the stringent allowance for the presence of very low CO2
level endorsed the modification of the process design. The new Hi-Pure design combines the

17

amine solution and carbonate solution process to enhance the rate of CO2 absorption (Rufford et
al., 2012).
Another kind of technology called the hybrid absorption process technology has been
developed where the effects of physical and chemical absorption processes have been combined
in a single unit operation by using mixed solvents. Sulfinol-D licensed by Shell Global Solutions,
Sulfinol-M, Amisol process licensed by Lurgi are some of the well known hybrid absorption
processes. (Rajani, 2004, Kohl and Nielsen, 1997).

1.2.3 Adsorption
The process of adsorption can be described as the adhesion or retention of selective components
of feed gas stream brought into contact to the surface of certain solid adsorbent as the result of
the force of field at the surface. The reverse process is known as desorption in which the
adsorbed foreign molecules are released. High pressure and low temperature is favorable for
adsorption whereas low pressure and high temperature is suitable for regeneration or desorption.
In natural gas industries, removal of water, sulphur, mercury and heavy hydrocarbons are carried
out based on adsorption. Although adsorption process is rarely applied for bulk separation of
CO2 from CH4, there are kinetics-based adsorption processes that have been implemented in
USA for the recovery of methane from landfill gas. These gases mainly comprises of methane
(50-65%), carbon dioxide (35-50%), a trace amount of nitrogen and sulfur compounds. In this
process, carbon molecular sieve is used as the adsorbent. In use of this process, it can be possible
to recover more than 90% methane with 87-89% purity (Yang 1997, Tagliabue et al., 2009).
Depending on the nature and strength of the surface forces, adsorptive gas separation process can
be divided into two types a) physical adsorption and b) chemisorption. In physical adsorption
the gas molecules are adsorbed in the surface pores, there is no chemical reaction associated with
it. In chemisorption there is a formation of a chemical bond between the sorbate and the solid
surface (covalent interaction of CO2 and the surface of the adsorbent) which facilitates larger
adsorption capacity. These kinds of interactions are strong, highly specific, and often not easily
reversible. Chemisorption is sometimes employed for removal of trace concentrations of
contaminants. However, the difficulty of regeneration makes such systems unviable for most
process applications. The forces of physical adsorption are weaker (a combination of Van der
Waals forces and electrostatic forces) than the forces of chemisorptions which means the heats of

18

physical adsorption are lower. Since there is no covalent bond formation the adsorbent is more
easily regenerated. Physical adsorption at a surface is so fast, and the kinetics of physical
adsorption is usually controlled by mass or heat transfer rather than by the intrinsic rate of the
surface process (Meyers 2001).Based on regeneration methods, adsorption process is most
commonly divided into temperature swing adsorption (TSA), pressure swing adsorption (PSA)
and displacement desorption. In TSA, desorption is achieved by increasing the temperature of
the adsorption bed, either by applying heat to the bed or by purging with a hot purge gas.
Thermal swing adsorption is very reliable to remove minor component. The main limitation is
the adsorption cycle time that is required to cool down the bed. Moreover, high energy
requirements and large heat loss are on the cards. (Mersmann et al. 2011). PSA is a well known
technology for the removal of CO2 from gaseous streams containing methane. In PSA,
regeneration is carried out by lowering the operating partial pressure to desorb the adsorbate
(Kerry 2007). This can be obtained either by depressurization or by evacuation or by
implementing both. It

is more suitable for bulk separation. Another type of desorption is

Displacement desorption. It is similar to purge gas stripping as the temperature and pressure are
maintained constant, but instead of an inert purge, an adsorbable species is used to displace the
adsorbed component from the bed. It is generally used when desorption by pressure swing or
thermal swing fails to be practical. Fluidised and moving bed operations (Seader and Henley,
2006), and fixed- bed electrothermal-swing adsorption (ESA) (An et al., 2011; Grande and
Rodrigues, 2008) are some of the less commonly applied adsorption techniques. The most
important factors for sustainable application of this technology are a) high selectivity and good
adsorption capacity of the target component, b) high surface area available for adsorption, c) fast
adsorption/desorption rate, d) physical and chemical stability, e) high regenerability and f) cost
of the adsorbent. Most commonly used commercially available adsorbents are - Activated
carbon, zeolites, molecular sieves etc. However, some novel adsorbents has been developed for
higher CO2 adsorption capacity Metal-organic frameworks (MOFs), zeolitic imidazolate
frameworks (ZIFs), surface functionalised silicas and porous carbons. Despite of novel
innovations and improved application specific researches this technology possesses some
disadvantages a) Very large, thick walled and heavy weighted adsorption tower which needs
high maintenance cost, b) low CO2 selectivity and adsorptivity of the available adsorbents, c)
high cost and low efficiency of CO2 adsorption in natural gas industries and d) production of

19

large amount of waste water and sludge (Hao et al., 2011,

Biruh Shimekit and Hilmi

Mukhtar 2012, Mullick 2014 ).

1.2.4 Membrane Technology


A membrane is a thin barrier placed between two phases or mediums, which allow one or more
constituents to selectively pass from one medium to the other in the presence of an appropriate
driving force while retaining the rest (Binay K Dutta, 2009). The separation of gas mixtures
with membranes has emerged from being a laboratory curiosity to becoming a rapidly growing,
commercially viable alternative to traditional methods of gas separation within the last two
decades. Membrane gas separation has become one of the most significant new unit operations to
emerge in the chemical industry in the last 25 years (Prasad et al. 1994). The important criteria
for selecting membrane materials for gas separation are based on the following key factors (a)
intrinsic membrane permselectivity (b) ability of the membrane material to resist swelling
induced plasticization (chemical resistance, which is quite rare but mostly fulfilled by inorganic
membranes) and (c) ability to process the membrane material into a useful asymmetric
morphology with good mechanical strength under adverse thermal and feed mixture conditions.
The polymer membrane material should have good interaction and sorption capacity preferably
with one of the components of the mixture for an effective separation (Biruh Shimekit and
Hilmi Mukhtar 2012).The first large scale industrial application of gas separation membrane
came to the market in the year 1980. It was launched by Permea used for hydrogen separation
and it was called PRISM. Since that inception the business of membranes has grown into a
$150 million/year and it will continue to grow in the coming future. There has been a lot of
research on this topic for last three decades but not even 10 type of polymer is available for
commercial gas separation. Most importantly, these polymers were not specifically designed for
gas separation hence improvement in such area is important that can provide higher selectivity in
gas separation. Apart from this, membranes must be thermally and chemically stable, resistive to
ageing, plasticization (for polymeric membranes), cost effective and must be easy to scale up.
Membrane technologies evolved from the discovery of Acid gas removal technique from natural
gas. The removal of CO2 from natural gas is the only large scale membrane based process in
practice today. There are more than 200 plants have been installed and most of them are installed
by Kvaerner-GMS, Universal Oil Products and Cynara (Baker et al. 2004). Membranes used

20

for gas separation are mainly classified into three categories based on the structure and materials:
polymeric membranes, inorganic membranes and mixed matrix membranes. During the last two
decades dozens of new polymers have been described in the literature, which have been
developed for gas separation. The largest group among these are probably polyimides. Cellulose
acetate Ethyl cellulose, Polycarbonate, brominated, Polydimethylsiloxane, Polymide (Matrimid),
Polymethylpentene, Polyphenyleneoxide, Polysulfone are the other polymers which are of
practical importance for gas separation. Cellulose acetate, polysulfone and polyimides are by far
the most important polymers for gas separation membranes (Nunes and Peinemann 2001).
Based on the operating temperature whether below or above the polymer glass transition
temperature, polymeric membranes can further be classified as rubbery polymers and glassy
polymers. In spite of, simple flow configuration and low cost, these polymeric membranes
cannot compete the conventional amine solvent absorption process due to low permeability, less
selectivity, degradation over time, non resistive against corrosive and high temperature
environment, unable to handle large volume of gas stream, low thermal and chemical stability.
Another major problem with polymeric membranes is the probability of plasticization of the
membrane after a limit of pressure of CO2 (Tin et. al., 2004, Larikov et. al., 2011, Rufford et
al. 2012). The current market for inorganic membranes for gas separation is extremely small. It
is not believed that the market share of inorganic membranes will increase significantly in the
near future. The main obstacle is their high price and some principle difficulties during
reproducible large-scale production. On the other hand fascinating research results have been
published in the recent past such as, unmatched selectivity for carbon dioxide/methane
separation with ceramic membranes (Tsai et al. 2000). There are different types of inorganic
membranes like ceramic membrane, nanoporous carbon membrane, Perovskite-type oxide
membranes etc. Dense inorganic membranes are prepared by spreading a thin metal layer of
palladium, nickel, silver, zirconia etc. and since all of these are expensive metals, sophisticated
handling is required. Also, the high capital cost, unstable mechanical properties, low
permeability reduce the applicability extensively. Ceramic, carbon and zeolite membranes are
commonly used for CO2/CH4 separation. A new development in the field of inorganic
membranes is zeolite based membranes. Silicalite-1 MFI membrane, Y-type zeolite membrane,
SAPO-34 zeolite membrane, KY-type zeolite membrane, DDR type zeolite membrane, A-type
zeolite membrane and T-type zeolite membrane (Yeo et al, 2012) are various types of zeolite

21

membranes which can be applied for CO2 separation from CH4 based on competitive adsorption.
Several obstacles such as expensive material, difficulty in producing the thin porous structure,
insufficient mechanical strength necessitates further research and investigation for successful
deployment in industries. Due to the different drawbacks of the existing membrane processes, it
is highly desirable to provide an alternative cost effective membrane which combines
homogeneously interpenetrating polymeric matrices for ease of processibility and inorganic
particle for high permeability and selectivity well above the upper-bound limit (Shekhawat,
Luebke et al. 2003, Biruh Shimekit and Hilmi Mukhtar 2012).). The combinations of the
superior gas selectivities of molecular sieves with the processibility of polymeric membranes
have attracted many researchers. The hybrid membranes consisting of inorganic molecular sieves
and polymers are often referred to as mixed matrix membranes (Mahajan and Koros, 2000,
Nunes and Peinemann 2001). It is still in developmental stage. The major challenges for
successful exploitation of membrane technology are a) high permeability and b) high selectivity.
Natural gas obtained from geological sources is at a high pressure. Hence high driving force is
there for permeation. But flue gas is generally at a low pressure. Therefore, high compression is
needed for permeation through membrane which makes the process overall process expensive
(Mullick 2014).

1.2.5 Cryogenic Technology


Cryogenics is the science that studies the production and behavior of materials at very low
temperatures spanning the range between 100 K (-173oC) and absolute zero (0 K or -273oC). The
word cryogenics has been derived from two Greek words cryos which means icy cold and
genes means born i.e. "the production of freezing cold"; however, the term is used today as
a synonym for the low-temperature state. And with the chaos around the world with crude oil the
demand of natural gas have increased. This has stimulated the researchers and they have shown
the anarchy to develop, design and modify cryogenic technology for Natural Gas separation. Of
course, a novel method which can simultaneously capture, remove and transport carbon dioxide
holds enormous promises for real life industrial applications. Cryogenic technology is
advantageous over other existing amine absorption or PSA/TSA based processes A) No
chemicals and solvents are required by the process, hence no recurring consumable costs; B) No
process makeup water supply and further treatment are required; C) No process heating systems

22

are required; D) No solvent regeneration equipments are required; E) Water is removed


immediately downstream of the inlet separator so corrosion potential is scant; F) carbon dioxide
is available at higher pressure and can be used for Enhanced Oil Recovery or sequestration
purposes; G) Natural Gas Liquids (NGL) obtained as a by-product which has good market
potential; H) There is no chances for foaming and I) No special winterization requirements for
cold climates. Moreover, if process integration is employed and the required cold duty is
obtained at relatively low costs from a liquefied natural gas (LNG) re-gasification terminal,
cryogenic carbon capture becomes extremely attractive and economically feasible. Despite of so
many advantages, this technology still could not replace the conventional processes described
before. The main reason for this is the high cooling cost for the process. At atmospheric pressure,
CO2 directly de-sublimes from gas phase to solid phase below the saturation temperature. But for
operation in the gas-liquid zone, high compression of the feed gas is necessary which increases
the capital cost. Another problem is the solid formation, often columns are plugged by solid CO2
clusters and ice that comes from the water vapor freezing in the CO2 feed mixture. That is why,
the researchers are currently motivated to develop and establish the desublimation process
industrially (Mullick 2014).
The cryogenic technology can be classified into two major sections a) Conventional Cryogenic
Technologies and b) Non-conventional Cryogenic Technologies. In the next chapter, these
technologies have been discussed in details.

23

1.3 Research Methodology


The work was carried out as follows
Firstly, a detailed literature review was carried out. More than 80 sources of literature including
journal papers, conference proceedings, thesis works, books, articles and websites have been
reviewed. The references cited in each relevant literature were examined to find out additional
sources of information.
Secondly, the research gap was identified from the detailed literature review and the research
questions were formulated.
Then, according to our research question, the work was divided into two sections a)
Experimentation and b) Transport phenomena modeling and Simulation. The work being a joint
collaboration between Universiti of Tecknologi PETRONAS and Jadavpur University, the
experimental part was carried out at Universiti of Tecknologi PETRONAS and the transport
phenomena modeling and simulation were carried by us at Jadavpur University.
Experiments were conducted in a setup at different initial bed temperature profiles both in
counter current and co-current configurations. Feed composition, flowrate and initial temperature
were varied and experiments were conducted.
Then, a two step transport phenomena model was developed considering a single packing to
study the spacio temporal evolution and kinetics of the frost layer on a single packing, which
was further used to compute the frost layer of the total packed bed.
Thereafter, the model equations were solved using the GEARs algorithm (ode15s library
function available in MATLAB) in MATLAB considering a pseudo homogeneous state. The
initial bed temperature profiles obtained from the experiments has been used for the simulation.
The results obtained were analyzed to study the spacio temporal evolution of frost layer and to
predict the frost layer kinetics.

24

CHAPTER
2
LITERATURE REVIEW

25

2.0 Historical Background


It is believed that the first ever successful liquefaction of any cryogenic gas was carried out not
earlier than 1877, by a French mining engineer Cailletet who produced a mist of liquid oxygen
droplets. He succeeded in pre-cooling a container filled with oxygen at 300 atm and then
expanding the gas by suddenly opening the valve of the container. Around the same time, a
Swiss physicist Pictet was also independently successful in liquefying oxygen by cascade
cooling.
A breakthrough was made in London in 1892 when James Dewar developed the vacuum
jacketed double-walled containers with silvered inner walls. This invention facilitated successful
liquefaction of hydrogen and helium in large quantities by 1898. In the mean time, Linde was
granted a patent on air liquefaction in Germany in 1885 and became the pioneer in industrial
scale production of cryogenic liquids.
In 1902, a French engineer Claude established L Air Liquid to develop and produce his
air liquefaction system in which a large fraction of cooling was obtained by using an expansion
engine. Five years later, in 1907, Linde installed the first air liquefaction plant in the USA.
During the period between the two World Wars, a number of developments took place in the
field of cryogenics. After the World War II, in 1947, Collins, a mechanical engineer, developed
an efficient cryostat for liquefaction of helium at MIT, USA. This could be used for safe and
sustained maintenance of temperature for experimental studies between ambient and 2 K. The
impact of this development was so remarkable in boosting the confidence level of researches
engaged in cryogenic applications that anything earlier than this era was jocularly referred to as
BC or Before Collins. The newer developments are continually taking place even today
(Mukhopadhyay 2010).

2.1 Detailed Literature Review


A huge number of literatures are available on carbon dioxide capture and recovery technologies
based on cryogenic separation. Extensive study showed that these technologies can be classified
into three categories - (A) Conventional cryogenic technology, (B) Non-conventional cryogenic
technology and (C) Hybrid technology. Other than the technological aspects, the internal
thermodynamics and the science associated with the governing phenomena have also been

26

considered in this review of reported studies. The following sections have been developed to
give a brief idea on the subject considered in this thesis.

2.1.1 Thermodynamics and Solidification


The research on Natural gas purification using cryogenic technology is totally based on
the science of Thermodynamics. The Cryogenic Technology finds its origin in the Second Law
of Thermodynamics. And then there is Equation of State that describes the properties of fluid
mixtures and provides the mathematical relationships between the state functions associated with
the process. Concern toward understanding of the mechanisms of these technologies and the
proper design of the equipment necessitates a deep look into the thermodynamic analysis of CO2
- natural gas phase equilibrium.

Fig.9: Pressure Temperature Phase Diagram for CO2

The above figure shows the Pressure Temperature phase diagram for pure Carbon
Dioxide. It clearly shows that at higher pressure within the cryogenic limits, the CO2 becomes
solid. The general or conventional cryogenic distillation columns operate at a higher pressure and
often the solidification of the CO2 becomes a problem for the Heat Exchangers associated. That
is why the non-conventional ones are operated at normal atmospheric or lower pressure and to

27

eliminate the problem of solid CO2 packed beds are employed. In the latter, the zone of operation
is the Solid vapour region of the phase diagram.
Thermodynamic data for the methane-carbon dioxide binary system is available at three
primary sources in literature. These data sets also include the solid-liquid-vapour region of the
binary mixture. The first set of data was reported by Donnely et. al. (1954). This data includes
three phase data points from -78.6 to 57.78 0C. Critical conditions for CH4-CO2 system were
also presented. Different data points for SLE were also measured. Vapour liquid equilibrium for
different pressure ranges was also determined. Pikaar (1959) provided the second set of data. A
constant volume cell was used to measure the 1, 3, 5, 10 and 20 % CO2 frost lines along with the
dew and bubble point lines of theses mixtures in the region of three phase locus. Davis et. al.
(1962) measured the three phase locus for the binary mixture from the triple point of carbon
dioxide to -175.61oC. In addition to that they also measured the composition of vapour and liquid
phase along the solid-liquid-vapour locus of methane carbon dioxide system. Eggemen et. al.
(2005) found that unreliable CO2 freezing temperature predictions are being made by several of
the commercial process simulators typically used by gas processors. In general, they found the
existing experimental data were adequate and that thermodynamic models, both equation of state
and activity coefficient based, can be used to make accurate predictions of CO2 freezing
temperatures. However, previous works was not adequately addressed how to properly apply
these models within a process simulation. According to them it was the improper formulation of
the CO2 freezing calculations was the cause of the unreliable predictions made by the
commercial process simulators. They showed how to properly formulate the thermodynamic
calculations to be used for prediction of CO2 solids formation. Procedures for heat exchangers,
expanders and columns have been discussed. Common pitfalls (convergence to spurious roots,
convergence to physically meaningful but useless solutions, non-convergence of numerical
algorithms, improper formulation of temperature safety margins, etc.) can be avoided by using
these procedures.
Many other phase equilibrium experimental data for CO2 is available in literature. A summary of
this is given below.

28

Table 3: PVTX experimental data for carbon dioxide mixtures (Maqsood et al. 2014)
Source

Year

Type

Mixture

Temperature range

Pressure range

( C)
Donnelly and Katz

1954

TPxy

CO2-CH4

1968

TPxy

CO2/CO, CO2/Ar, CO2/CH4,

(bar)
-106 to 29

20-74

(1954)
Kaminishi et al.

- 50 to 10

24-200

CO2/CO/H2

(1968)
1968

TPxy

CO2-CH4

-65, -228 to -53.15

440-690

Arai et al. (1971)

1971

PVTX

CO2-CH4, CO2-N2

-20 to 15

50-150

Sarashina et al. (1971)

1971

PVTX

CO2-CH4-N2

-40 to 0

60-100

Davalos et al. (1976)

1976

TPxy

CO2-CH4

-43 to -23

9-85

Hwang et al. (1976)

1976

TPxy

CO2-CH4

-120 to -54

20-65

Mraw et al. (1978)

1978

TPxy

CO2-CH4

-184 ton -65

5-63

Somait and Kidnay

1978

TPxy

CO2-CH4, CO2-N2

-3

30-120

1983

TPxy

CO2-CH4, CO2-N2, CO2-CH4-

-54 to -23

5.8-160.15

Neumann and Walch


(1968)

(1978)
Al-Sahhaf et al.

N2

(1983)
Magee and Ely (1988)

1988

TPxy

CO2-CH4

-48 to 127

20-350

Ely et al. (1989)

1989

TPxy

CO2-CH4, CO2-N2

-23 to 57

23-320

Trappehl and Knapp

1989

TPxy

CO2-CH4, CO2-N2

-53

20-120

Al-Sahhaf (1990)

1990

TPxy

CO2-CH4-N2

-43 to -23

62.1-100.34

Xu et al. (1992)

1992

TPxy

CO2-CH4, CO2-N2, CO2-CH4-

15 and 20

51.1-91.1

50-250

199-999

(1987)

N2
Seitz et al. (1996)

2002

PVTX

CO2-CH4-N2

2.1.2 Conventional Cryogenic Technology


Conventional Cryogenic Technology is a very old process where the operation is carried out at a
very low temperature. Conventional Cryogenic Technology includes simple Cryogenic
distillation and extractive distillation. Cryogenic distillation is carried out at an extremely low
temperature and high pressure to separate CO2 and other components based on their different
boiling point. This method directly produces liquid CO2 or CO2 vapor at a high pressure which
reduces extra costs of compression for storage purpose. This technology is not economical and

29

energetically viable for dilute gas streams. One of the major operating problems for this method
is solid formation and choking of column in the older top section of the distillation columns in
both low and high pressure ranges. Solid formation during separation of CO2 has been reported
in literature (Katz & Donnely , 1954). Gas Processors Association (RR-10, 1974) published
liquid phase composition of CO2- CO4 binary gas mixture at S-L-V locus. Maqsood et al. (2014)
predicted the solid formation in the distillation column inside the convergence look utilizing
GPA the data they found that increasing the column pressure might be help full to avoid solid
formation. However methane loss will increase and the purity of methane will be questionable.
Henson et al. (2001) derived a low order wave model for cryogenic nitrogen purification
column and compared the MATLAB simulated results with a first principles model developed
within the commercial dynamic simulator HYSYS. Plant (Hyprotech). The authors used the non
linear wave modelling concept to model the cryogenic nitrogen separation column and
performed rigorous modelling of the combined reboiler/condenser assembly and verified the
model using the dynamic simulator. The model is capable of producing acceptable prediction of
composition responses for various types of disturbances. However, the constant wave pattern
assumption used in the wave model development invariably leads to some degree of modelling
error. They proposed on-line model adaptation as a possible approach to overcome the constant
wave shape assumption. Panopoulos et. al. (2013) suggested a cryogenic method for recovery
of H2 and CH4 from a rich-CO2 stream in a pre-combustion carbon capture system. They
modeled their process using Aspen Plus based on differences in thermodynamic properties and
evaluated the effects of it on the efficiency of the system. They also studied the effect of
operating parameters of the (Purification & Compression Unit) PCU integration on the
performance of the system. Maqsood et. al. (2014) synthesized efficient cryogenic distillation
sequence for purification of natural gas having medium and high concentration of carbon dioxide
contained. Calculations for conventional and hybrid distillation column sequences were
performed using the heuristic and evolutionary strategies. Three different sequences direct,
indirect and mixed were chosen for different feed compositions selected from the literature. It
was found that direct sequence is the best options for separation of CO2 from natural gas with
different feed composition in respect of minimum vapour flow, marginal vapour flow and energy
requirements. They also found hybrid cryogenic network requires considerably lower energy

30

and showed significant reduction in capital cost of the columns compared to the conventional
cryogenic network.
Maqsood et. al. (2014) presented a techno- economic evaluation of cryogenics network for
separation of carbon dioxide from natural gas with different feed compositions. Equipment
sizing and cost estimation has been carried out for the cryogenic networks using the co relations
provided in the literature.
Maqsood et. al. (2015) conducted a study with different configurations of cryogenic distillation
networks to remove carbon dioxide from natural gas feed with high heavy hydro carbon
contained they investigated three different case studies along with conventional cryogenic
network. They found that higher operating pressure leads to reduction of energy requirements but
operational problems in distillation columns can arise due to thermodynamic behavior of
methane - carbon dioxide system.
Extractive Distillation
In order to prevent solid formation inside the distillation column extractive distillation is
a suitable option. Holmes et al. (1982) patented and extractive distillation process, introducing
heavier hydro carbon (C2-C5 alkanes) or other non polar liquids which are miscible with methane
at the column conditions in the condenser section of the distillation column. This help to avoid
solidification of carbon-dioxide. Holmes et al. (1983) executed pilot studies on cryogenic acid
gas / hydrocarbon separation process and validated the work. Valencia et al. (1985) patented a
method for separating carbon dioxide from methane using Helium as an additive which
facilitated the separation process and prevented solid carbon dioxide formation. However the
separation of He from CH4 at higher pressure is quite problematic. Atkinson et al. (1988)
introduced a dual pressure distillation process intended for the removal of high concentration
carbon dioxide from methane. It comprises of two distillation columns operating indifferent
pressure to avoid carbon dioxide solidification. ZareNezhad et al.(2009) reported an extractive
distillation technique for producing CO2 enriched injection gas for enhance oil recovery (EOR)
fields. No external solvent is required in this case. In this technique a part of natural gas liquid
stream comprising of iso-butane and heavier components were added to the top of a CO2 stripper
followed by ethane and propane stripping of ethane and heavier components stream. Due to this
the azeotropic mixture of carbon dioxide and ethane breaks down which increases the tray
efficiency. Berstad et al. (2012) reported presented a low-temperature process for CO2 removal

31

from natural gas before liquefaction. They simulated a three distillation column network by using
C5 as an additive in ASPEN Hysys with PengRobinson equation of State for the separation of
CO2 from natural gas. Berstad et al. (2013) presented a review on low temperature carbon
dioxide technologies and discussed their potential. This gives us detailed idea about the
applicability, energy efficiency of the technologies discussed with the base line technology.

2.1.3 Non-conventional Cryogenic Technology


There is always an alternative way to everything as they say that the grass is always greener on
the other side. Researchers found a few alternative ways to discover the real potential of the
cryogenic technologies. These alternative things are referred to as the Non-Conventional
Cryogenic Technologies. These non-conventional cryogenic technologies focuses on separation
of carbon dioxide by utilizing one of the major disadvantages of the conventional cryogenic
processes into its working principle. Actually the solidification of CO2 in the solid vapour zone
is utilized to desublimate carbon dioxide from the gas stream.
Schah et al. (2011) conducted a feasibility study of Carbon capture by desublimation. They
modeled the process using ASPEN Plus featuring finned-plate heat exchangers. The process
cooled the incoming flue gas with a condensing heat exchanger and there after another heat
exchanger desublimated the remaining water vapour in the flue gas. Finally a third heat
exchanger desublimated the Carbon dioxide. In this model, both water and carbon dioxide froze
and desublimated directly on the heat exchanger surface there by requiring periodical
regeneration of the heat exchanger.

An economic analysis compared to a common MEA

absorption showed that this desublimation process has superior capture performance that requires
comparatively less energy penalty. A continuous process that avoids losses due to regeneration
employee parallel heat exchanger trains makes it really attractive. Clodic et al. (Clodic et al.
2005; Clodic and Younes 2002; Clodic and Younes 2003; Perrotin and Clodic 2005; Clodic
and Younes 2006; Clodic and Younes 2006) have patented a desublimating carbon capture
system quite similar to the one that Schah model. Schahs design employs a series of heat
exchangers that operates at successively decreasing temperatures. The first one condenses water,
the latter remaining water vapour and the last one desublimates carbon dioxide. Clodic uses a
flat-plate heat exchanger for the desublimating stage instated of the finned heat exchanger as

32

used by Schah. The cold and clean flue gas exits the last exchanges going through a regenerating
heat exchanger to cool the incoming flue gas. After the CO2 & the H2O loading in the heat
exchanger reaches a maximum, the flue gas is diverted into a parallel system. Then the heat
exchanger enters the regenerations mode. During this period valves isolate the frozen CO2 as
they warm up. This melts the CO2 and pressurizes the system. The water and CO2 flow out of the
heat exchanger as liquids under pressure. The heat exchanger pressure drops back to that of the
flue gas, the heat exchangers cool back to cryogenic temperatures; and there by resuming the
process. Certain challenges exist in the work of Clodic. They are - (1) The sublimating CO2
creates an insulating layer between the heat exchanger and the flue gas decreasing the heat
transfer and increasing the pressure drop; (2) the system is inherently a semi-batch or batch
process; (3), the amount of CO2 that is captured is small compared to the mass of the heat
exchangers on which it collects, and cycling the large mass of heat exchanger material from the
capture temperature of around 140 K to the CO2 melting temperature of about 220 K generates
large amounts of entropy and decreases the process efficiency and (4) pressurizing the heat
exchangers at commercial scale will require a valve that sustains 8-70 bar pressure in a duct that
is nominally 30 feet in diameter, which presents a significant practical (rather than fundamental)
problem.
Cryogenically Cooled Packed Bed
Tuinier et. al., (2010, 2011) has developed a novel process concept for carbon capture and
storage based on dynamic packed beds with a moving interface between water and carbon
dioxide. The process concept is based on the periodic operation of cryogenically cooled packed
beds. The process cycle consists of three consecutive steps cooling, capture and recovery steps
respectively. A front of desublimating- sublimating CO2 is formed and it moves based in the
temperature profile inside the bed. Nitrogen initially cools the packed bed. Once flue gas enters
the packed bed, water condenses and freezes, then CO2 desublimates onto the packing material.
As the bed reaches maximum H2O and CO2 loading, the flue gas is diverted to a parallel system
and pure CO2 flows into the bed above the desublimation temperature but below the freezing
temperature of H2O. The solid CO2 in the bed sublimates and leaves with the CO2 stream. Warm
nitrogen then evaporates the water, followed by a recycle steam of cold clean flue gas to cool the
packing material. After the capture cycle, the bed is regenerated for further use. The process was

33

reported for atmospheric pressure separation of low CO2 flue gases using dynamic beds. This
process can be made continuous if three columns are built in parallel. The temporal evolution of
axial temperature, concentration, and mass deposition profiles occurring in the beds can be well
described by a validated one-dimensional pseudo-homogeneous axially dispersed plug flow
model. Aliredza (2013) reported the experimental and simulation work on recovery of CO2
using cryogenic packed bed. Figure 9 shows the schematic representation of cryogenic packed
bed. Abul Hassan et al. (2013) developed an experimental setup for cryogenic separation of
CO2 from natural gas with high CO2 content. In this study, the CO2 concentration was used up to
70%. The separation principle of CO2 from natural gas was based on desublimation principle in
countercurrent cryogenic packed bed. They also simulated the cryogenic packed considering a 1
dimensional pseudo homogeneous model (Abul Hassan et al. 2013). Due very steep gradients
of temperature and concentration the solution is tough to get. Finite difference, Forward-Time
Central Space (FTCS) scheme is used for simultaneous numerical solution of the model. The
scheme was found to be efficient as the results compared with the experimental ones showed
promising potential for industrialization. Multiple cryogenic packed beds have been used for
simultaneous dehydration as well as CO2 separation by Karen (Karen Hui, 2013) and Abul
Hassan et al. (Abul hassan et al., 2014). Aditi Mullick (2014) have modeled and simulated the
separation of CO2 onto cryogenically cooled packing using reduced order transport phenomena
models. The transport mechanism and dynamics of cryogenic CO2 capture have been addressed
using a model based on single packing. The nucleation kinetics and growth rate of deposition of
CO2 frost on a single cooled packing is studied using a two-step model, which takes into account
the diffusion from supersaturated gas phase to the gas solid interface and relatively slower
crystallization kinetics and nucleation on a heterogeneous surface (packing) in series. Recently,
Abul Hassan et al. published a paper where they have explored the minimization of energy
consumption for a counter current switched packed bed intended to separate CO2 and other
components of natural gas (Abul hassan et al., 2014). They conducted experiments with a
switched packed bed setup by changing different operating parameters and compared the results
with other co-current or jacket cooled constant temperature configurations. They also
investigated the effects of the important process parameters initial temperature profiles of the
cryogenic bed, feed composition, and feed flow rate on energy requirement, bed saturation, bed
pressure and cycling times. The energy consumption of countercurrent switched packed bed was

34

compared with the conventional cryogenic distillation process and it saves 662 kJ energy per kg
CO2; for a constant inlet feed composition. The effect of feed composition on the energy
requirement revealed that countercurrent switched cryogenic packed beds have potential for
substantial energy savings during purification of natural gas with high CO2 content.
Stirling Coolers
Song et al. has developed a cryogenic carbon capture technology similar to Clodic, but has
managed to make it a truly continuous process (Song, Kitamura et al. 2012; Song, Kitamura et
al. 2012; Song, Kitamura et al. 2012; Song, Kitamura et al. 2013). Song uses a similar three
heat exchanger design but uses Stirling coolers (SC) instead of plate heat exchangers. A Stirling
cooler generates an acoustic pulse that creates a refrigeration effect inside a pulse tube cold
finger (Hu, Dai et al. 2010). Stirling coolers have high efficiency, high reliability, and small
footprint and volume. The first SC pre-cools and dehydrates the flue gas. The condensed water
leaves as a separate stream, while the cool flue gas continues to a second SC. The second SC
desublimates the CO2 as a solid on the surface of the cold finger, while the clean flue gas
exhausts. A mechanical scraping rod is used to keep the surface of that heat exchanger clean,
while solid CO2 falls into a storage chamber where at third SC provides cooling to keep the CO2
in a solid state. Song et al., (2013) evaluated the properties of this free piston Stirling cooler
system and briefly compared its performance with other cryogenic methods. They found that this
approach is better than LN and LNG in terms of energy consumption but high pre-chill time,
vibration and less deposition area are disadvantages for this system. They suggested integrating
this method with amine methods is an effective approach. They are looking forward to make this
a vibration proof system. Song et al. (2013) experimentally tested the performance of the Free
Piston Stirling Cooler (FPSC) system for CO2 capture. The effect of flowrate of the gas stream
and temperature of FPSC was investigated in detail. They found that the system can capture 95%
CO2 from simulated flue gas and consume 0.55MJ of electrical energy per kg of carbon dioxide
recovered which is the least compared to other dominant technologies. Song et al., (2014)
presented a process simulation and energy analysis of cryogenic CO2 capture process based on
Stirling coolers. They simulated the overall energy flow Stirling coolers based cryogenic CO2
capture process. Theoretical analysis of the energy consumption for each of the unit in the
capture system was also under taken. They also compared energy consumption of this process

35

with other established technologies and claimed there process to be least energy consuming (1.6
MJ/KG CO2). Furthermore; they extended their work and investigated the influence of capture
conditions on the performance on the systems; based on three levels and variables and in central
composite design. They optimized the system with the objective of maximum CO2 recovery,
CO2 productivity and minimum energy consumption. They compared there result with
experimental data. They found that under the optimal condition 95.20% CO2 can be removed.
Song et al., (2015) investigated the Co-efficient Of Performance (COP) of the Fitted Piston
based Stirling coolers (FPSC). The key parameters were also investigated in order to improve the
COP. It was found material of construction, length and diameters of the cold head as well as the
ambient temperature and humidity have certain influences on the COP of the FPSC. Despite of
their high COPs, the COP of the system was around 0.7 due to other energy consumption units
like vacuum pump and control panel. While Songs technology is innovative and has improved
upon previous cryogenic technologies, it is still very new with work still needed, especially in
the area of scale up.

2.1.4 Hybrid Technology


CFZ Technology
An Exxon Mobil pilot plant was used by Northrop et. al. (2009) for the study of the CFZ
technology applied for the cryogenic separation. It showed improvements when CFZ technology
was integrated with existing cryogenic distillation columns. The liquid stream coming from the
upper rectification section enters the CFZ section where it comes in contact with the methane
stream at a low temperature below -80o to 90o C. The CO2 present in the liquid stream solidify
and separates from the methane stream. The solid CO2 drops below where it melts again on a
melting tray and enters the stripping section below. However, the main disadvantage of using
direct heat exchange between the inlet gas and refrigerated cold fluid with or without heat
exchangers is that no water can be tolerated in the inlet stream in order to prevent plugging by
ice causing operational hazards. In addition the build up of any solid CO2 or ice on to heat
exchanging surfaces causes a decrease in the heat transfer rate and thus a decrease in overall
process efficiency. The addition of the molecular sieve dehydration unit adds substantial cost and
volume to the platform based operation.

36

Cryocell Process
Hart et al. (2009) proposed and tested the Cryocell process. The feed stream of natural gas
containing CO2 at normal temperature is first cooled at constant pressure up to a temperature just
above the freezing point of CO2. The feed mixture will be condensed into a liquid phase. The
liquid mixture is then flashed through a Joule- Thomson Valve at constant enthalpy by which the
liquid splits into solid, liquid and vapour phases. CO2 exits as pure solid CO2 and also as liquid
and vapour phases. The operating conditions should be such that the vapour phase becomes lean
in CO2 whereas the liquid phase becomes rich in CO2. The phases are then separation in Cryocell
separators. Demonstration plants have been established for commercially exploiting the Cryocell
technology and several test runs were carried out varying the CO2 concentration in feed gas from
3.5 to 60 mole%, inlet feed gas temperature ranging from -50 to -65 C at a feed pressure of
5500 to 6500 kPa. The available literature on this method unfortunately does not provide
modeling or fundamental studies and generation of mass transfer data, freezing kinetics or other
fundamental details due to commercial reasons.
Condensed Contaminant Centrifugal Separation
Willems et. al. (2010) developed a mechanical method for separation of CO2 from the natural
gas. The process is known as C3sep (condensed contaminant centrifugal separation), in which
CO2 is condensed into droplets and then separated from the natural gas using rotational
separators. Condensed contaminants centrifugal separation of carbon dioxide is a new process
concept which has been developed on the basis of semi-cryogenic distillation along with
mechanical centrifugation. Specially designed turbo-expanders are used to cool down process
streams by expanding it. Due to different boiling point ranges of different components of a gas
mixture, rapid cooling results in preferential condensation of the components at different times.
This leads to formation of mist with very small droplets of diameter in the range of 1-10 m. The
vapor-liquid mixture is then subjected to cyclone separating mechanism to separate the small
droplets from vapor phase.

37

Other hybrid technologies


Struchtrup et al. (2010) suggested a hybrid membrane and cryogenic process be utilized instead
for reduction of the overall energy requirements. The hybrid process uses an O2/N2 permeable
membrane to create oxygen enriched air. This enriched air is then turned into high purity oxygen
using cryogenic distillation. Several permutations were evaluated including a compressorturbine, vacuum pump, two-stage compression and two-stage membrane systems. They were
compared on a practical and thermodynamic level to the current cryogenic process in use. It was
found that the vacuum pump arrangement has potential to reduce energy requirements. It was
also found that this process is more suitable for small to medium scale productions. The effect of
the hybrid design on the oxy-fuel process was also analyzed and found to improve the process
efficiency by 0.9%.
Surovtseva et al. (2011) reported a combined cryogenic and hydrate method for CO2 capture
from IGCC flue gas. The technology is based on combination of to low temperature processes,
namely cryogenic condensation and the formation of hydrates to remove the carbon dioxide from
flue gas stream. The first stage of the technology is condensation at 218K and the second stage is
formation of solid hydrate at about 1o C using hydrate promoters. A trial experimental run
showed high purity CO2 (95-97 mol %) in liquid form.
Favre et al. (2012) investigated the potential for a hybrid process combining membrane and
cryogenic separation to achieve efficient post-combustion carbon capture. The hybrid process
combines a first step CO2 pre-concentration with a membrane unit and a second step CO2
cryogenic condensation. It was carried out via a simulation study. Three different CO2
concentrations was compared: 5% (typical of a natural gas turbine exhaust), 15% (coal power
plant flue gas) and 30% (steel plant or oxygen enriched air combustion). Three different
compression strategies and two membranes selectivities ( = 50 and 100) on the separation
performances has also been investigated for a required CO2 purity of 0.9 and a capture ratio
larger than 85%. The simulated results gave satisfactory results.

38

2.3 Research Gap


The reported literature on conventional and non-conventional cryogenic technology has shown
great potential for application in natural gas purification and further industrialization. Most of the
work has focused on carbon capture from flue gas (Tuinier et al. 2010, Hart et al. 2009, Song et
al. 2012). These works has been carried out at low pressure. The work of Tuinier et al., is at 1
atm pressure and it can be made continuous if three column are constructed in parallel. The work
of Song et al. is impressive and despite of being patented the operating pressure is not high, the
system is vibrational and extra mechanical energy is required for scraping off the solidified
carbon dioxide from the surface of the heat exchangers. The work of Abul hassan et al. have
made the process continuous with a cryogenically cooled packed bed while varying the different
operating parameters. They have also provided numerical solution to the stiff problem
considering a 1-D psuedo homogeneous model. Hence, maximum literature has focused on
overall model considering heat and mass balance equation of the overall bed. But literatures
discussing about the details transport phenomena inside the packed bed are scant and rather not
present. Also no literature was found that explained the frost formation kinetics considering the
nucleation of a carbon dioxide frost crystal on the packing surface. So the challenge to us is to
establish a model that can depict the spacio temporal evolution of the frost layer thickness and
also explain the frost formation kinetics, therefore explaining the detail transport phenomena
inside the packed bed. In this thesis, an effort has been made to face the challenge and bridge the
literature gap.

39

2.4 Objectives
Transport Phenomena modeling of the packed bed to study the spacio temporal
evolution of the frost layer and the frost layer growth kinetics on the packing surface.
Modeling and Simulation of a cryogenically cooled single packing using two-step model
of crystallization kinetics and heterogeneous nucleation on the packing surface to find the
rate of frost layer deposition on a single packing.
Modeling and Simulation of a cryogenically cooled packed bed embedding the rate of
frost deposition from single packing with pseudo-steady state mass and energy balance
equations for gas phase.
To study the influence of different operational variables flow rates, initial bed
temperature profile, flow configuration on the frost layer thickness, percentage
separation, frost deposition etc.
To study the effect of homogeneous nucleation in the output variables.

40

CHAPTER
3
MODEL DESCRIPTION

41

3.0 Problem Statement


Separation of carbon dioxide from flue gas streams using cryogenic technology has already been
reported. Different researchers around of world have taken different approaches to address the
carbon capture problem from flue gas. Stirling coolers, cryogenically cooled packed bed,
multiple cryogenic packed bed, hybrid cryogenic distillation network etc are some of the novel
approaches taken to mitigate the problem. Another issue, the ever increasing energy demand has
called for the invasion of potentially impure natural gas wells containing high amount of carbon
dioxide (as high as 75%). So it is also important today to process natural gas streams with high
carbon dioxide content. The basic theory operating behind these upcoming technologies is to
solidify carbon dioxide out of the flue gas stream, below the critical pressure by cooling down
the incoming hot flue gas stream at a cryogenic temperature. The CO2 desublimes either on heat
exchanger surfaces or on the cryogenically cooled packing and forms carbon dioxide frost layer.
Despite of so many novel approaches taken, the researchers have only found the extent of
separation, optimized parameters for a certain process energy penalties and have showed good
potential for industrialization. But no initiative has been taken to investigate what is happening
inside the system. More specifically, the kinetics of frost layer formation and growth on the
cryogenically cooled packing or on the heat exchangers surfaces has not been demonstrated yet.
The work of Abul Hassan et al., shows cryogenically cooled packed bed has enormous potential
to be used in separation of CO2 from natural gas. So the challenge to us is to model a
cryogenically cooled packed bed incorporating the effects of the frost formation kinetics and to
solve the problem that can describe the phenomena going inside the packed bed.

3.1 Nucleation Theory


Nucleation is a phenomenon of broad scientific interest and technological importance. Most
nucleation occurs heterogeneously unless the metastable parent phase from which the nuclei
form is perfectly homogeneous and isolated from any catalyzing medium. The ability to control
the process lies at the heart of the development of a novel microstructure or processing
technology. This is because nucleation controls to a large extent the initial reaction rate, structure
type, size scale, and spatial distribution of the product phases. Nucleation is usually
a stochastic process (Sear, 2007), so even in two identical systems nucleation will occur at

42

different times. The standard theory that describes this behaviour for the nucleation of a new
thermodynamic phase is called classical nucleation theory. Classical nucleation theory is the
most common theoretical model used to understand why nucleation may take hours or years, or
in effect never happen. This is the standard simple theory for nucleation of a new thermodynamic
phase, such as a liquid or a crystal.
The driving force for nucleation is the difference in the free energies of the initial and final
configurations of the assembly. When a spherical embryo of solid is formed in an undercooled
uniform liquid, first, there will be a change in free energy associated with the difference in the
volume free energy of the atoms in the solid and liquid. Secondly, there will be a number of
atoms occurring in the transition region between liquid and solid. These atoms will be in a high
energy state and are the origin of the surface free energy of the embryo.
In general, there are two types of nucleation a) homogeneous nucleation and b) heterogeneous
nucleation. Homogeneous nucleation refers to the case when no nucleation sites (e.g., foreign
particles, container walls etc.) are available in the system. In case of homogeneous nucleation,
the nucleation of a new phase occurs by the aggregation of components of another phase without
being influenced by impurities or external surfaces (Christian, 1975). There is virtually no
homogeneous nucleation in nature because there is always presence of a foreign surface.
However, when all potential nucleation sites are removed, homogeneous nucleation can occur at
a very large undercooling, e.g., liquid water exists to temperatures below 233 K (Liu, and Du,
2004). In the context of solidification, this requires a significant undercooling and it means that
the solid nuclei must form homogeneously from the liquid.
Heterogeneous nucleation refers to the case when there are nucleation sites existing in, or in
contact with, the metastable parent phase, where nucleation occurs on the surfaces of these
nucleation sites. In practice, homogeneous nucleation is difficult to occur as an extremely pure
assembly containing no structural defects is hard to produce. The size, geometry and surface
condition of these nucleation sites will significantly affect the nucleation process.

43

Fig. 10: Gibbs Free energy difference for homogeneous and heterogeneous nucleation

Heterogeneous nucleation is typically understood to be much faster than homogeneous


nucleation using classical nucleation theory. This predicts that the nucleation slows exponentially
with the height of a free energy barrier G [Fig. 10]. This barrier comes from the free energy
penalty of forming the surface of the growing nucleus. For homogeneous nucleation the nucleus
is approximated by a sphere but as we can see in the schematic of macroscopic droplets to the
right, droplets on surfaces are not complete spheres and so the area of the interface between the
droplet and the surrounding fluid is less than a sphere's 4r2. This reduction in surface area of
the nucleus reduces the height of the barrier to nucleation and so speeds nucleation up
exponentially (Ma, 2008).

3.2 Description of packed bed setup


The experimental setup designed for the research work consists of a packed bed. Marbles of
diameter of 1cm has been used as packing material. The whole setup is some sort of a miniature
double pipe heat exchanger. The inlet of the setup leads to a gas mixture chamber which enters
into the main chamber. The main chamber consists of two co-centric chambers. The inner one
consists of the packed bed; one end of which is closed and it is quite shorter in length from the
outer one which enhances an extra area for heat exchange purpose.

44

Fig. 11: The Packed Bed Experimental Setup

The outer one is like a jacket which is meant to be used for heat exchange with the packed bed
using refrigerant (in this case Liquid Nitrogen). The outer shell has two valves that controls the
input and output flow of the refrigerant. Moreover it is provided with a safety valve and a
pressure gauge. The outer shell leads to the outlet line which consists of a valve and product
collection chamber from which the desired product is collected.

3.3 Experimental Procedure


The experiment was carried out in a cryogenically cooled packed bed setup. A schematic
diagram of the cryogenically cooled packed bed is shown in the figure---. The whole experiment
can be divided into three stages or cycles. They are- (a) cooling cycle, (b) carbon dioxide capture
cycle and (c) regeneration of the cycle. In the cooling cycle the bed of spherical packing material
is cooled with liquid nitrogen at a cryogenic temperature. The next cycle is carbon dioxide
capture cycle. In this cycle a mixture of CO2 and CH4 of varying concentration is introduced in
the packed bed. The CO2 desublimates on the surface of the packing and methane passes through
without any phase change. When the bed was filled with frost layer of CO2 or when a small
quantity of CO2 was detected in the outlet, the supply of feed was cut off and the recovery of
CO2 started. In the recovery cycle, the frosted CO2 was recovered from the system by raising the
bed temperature above the freezing point of CO2 by introducing a CO2 stream at room
temperature.
The experiment was carried out at three different initial bed temperature profiles; both in counter
current and co-current configurations. The temperature profiles are given below.

45

3.4 Transport Phenomena Model for CO2 Separation on


Single Packing
A total bed of uniform stacked packing has been considered. From the total bed a single packing
has been considered of radius R. The main reason behind considering the single packing
modeling is to study the spacio temporal evolution and the frost layer deposition kinetics on a
single packing, which later has been embedded into the total packed bed to study the same of the
total packed bed.

Figure 12: Schematic diagram of a single packing with frost layer

A model has been developed for desublimation of carbon dioxide frost layer on a single cooled
packing from a relatively hot carbon dioxide gas. This model is basically two step model Mass
transfer from bulk gas to the interface of the packing and the kinetics of nucleation, which are
considered to be in parallel. Figure 12 shows the schematic diagram of a cryogenically cooled
packed bed with frost layer inside. Thereafter, a single cooled packing within the boundary layer
of the hot gas. The growth rate of the frost layer thickness () and variation of the interface
temperature are modeled considering a constant gas temperature.

46

3.4.1 Mass-transfer and kinetics of nucleation


The overall rate of mass deposition is combination of two steps in parallel: the rate of mass
transfer from the bulk gas to the interface and the rate of nucleation of the CO2 frost.
dm
k g Pb Pi 4 ( R ) 2 Mw k s ( Pi Psat )4 ( R ) 2 Mw
dt

(1)

The driving force for mass transfer from bulk gas to the interface is the difference in partial
pressure / degree of supersaturation ( P - Psat) from bulk to interface. Psat is the saturation vapor
pressure and is a function of the interface temperature, Ti.
First order kinetics with respect to the degree of supersaturation at the interface is considered to
describe the rate of nucleation of solid CO2 frost.
The rate constant for crystallization (Ks) can be written as:

E
G *
k s k so exp(
) exp( d )
kT
kT

(2)

G * is the activation energy for nucleation of crystals and Ed is the activation energy for the
*
diffusion. The activation energy barrier G for heterogeneous nucleation on packing surface

may be written as:


*

16 3Tm

3H c T 2

(3)

Where is the interfacial tension between the solid CO2 and gas, Tm is the saturation temperature
of desublimation on a flat interface, T is the degree of subcooling = (Ti - Tm) and H c is the
latent heat of crystallization per unit volume and is a negative quantity. f() is a function of
contact angle and can be written as:

f 0.25 1 cos 2 2 cos( )

(4)

Eliminating the interface pressure Pi, the overall rate of mass deposition can be written as
(t )

dm
d
4 ( R ) 2

K
y CO2 P P
4 ( R ) 2 Mw
frost
eff
b
sat
dt
dt

(5)

Where the effective mass transfer coefficient Keff is written as:

1
1
K e ff

kg
k s

(6)

47

Generally, the crystallization process involving the nucleation and phase change is relatively
slower process compared to gas phase mass transfer except very cold region and the overall
coefficient is dictated by the crystallization rate constant.

3.4.2 Energy-Balance Equation


The energy balance equations are written for the interface, the frost and for the packing.
Considering that the rate of heat accumulation inside the interface is negligible, the following
energy balance equation for the interface is:

dT f
kf
dr

4 R H s frost
r ( R )

d
2
2
4 R hTi Tg 4 R
dt

(7)

The rate of convective heat transport from bulk gas to the interface and the rate of generation of
thermal energy due to desublimation are balanced with the rate of conduction of heat from
interface to the frost layer towards the cooled packing (1st term).
A steady state conductive heat transport equation over the very thin frost layer with the boundary
conditions T=Ti at r=R+ and T=Tp at r=R gives the solution of the following form:

T Tp

r1 R
Ti T p
R r1

(8)

Tf= temperature within the frost layer; r1= radial distance from the surface of the packing
Considering a lump capacitance model the following energy balance equation is derived to
describe the rate of variation of packing temperature with time:

dT p
R
dT f
p Cp
kf
3
dt
dr

(9)
rR

Where, p, Cp and kf are the density of the glass packing, specific heat of the packing material,
and thermal conductivity of the CO2 frost, respectively.

48

3.4.3 Thermodynamic, mass and heat transfer correlations used for


simulation
The thermodynamic and transport correlations used at cryogenic temperature are given below.
The solid vapor saturation vapor pressure over a flat solid-gas interface is correlated with the
temperature. For using the following correlation:
= 10.257

= 26.876

= 25.957

= 25.311

= 26.335

= 51.60

.. 0.1% CO2

+ 4.08

0.022658 100% CO2

(10a)

........................70.5% CO2

(10b)

54.3% CO2

(10c)

. 18% CO2

(10d)

..10% CO2

(10e)
(10f)

The saturation vapor pressure for any concentration of CO2 in the binary mixture of CO2-CH4
has been calculated by using interpolation rule between the above correlations.
Saturation vapor pressure on a curved interface is correlated with the radius of curvature and
interfacial tension by the following relation:

2MH
p sat p sat exp

RT f

(11)

Where,
H is the mean curvature.
The saturation pressure psat is in mm Hg, T is in K.
The density of CO2 frost is
The conductivity of CO2 frost is

= 1562

= 0.7 .

The heat and mass transfer coefficient are calculated using the following correlations (Gunn
1978)

Nu 7 10 5 2 .1 0.7 Re0.2 Pr 0.33 1.33 2.4 1.2 2 Re0.7 Pr0.33

(12)

Sh 7 10 5 2 .1 0.7 Re0.2 Sc0.33 1.33 2.4 1.2 2 Re0.7Sc0.33

(13)

49

3.5 Transport phenomena model for CO2 capture using


cryogenically cooled packed bed with multiple packing
In this section, desublimation of carbon dioxide from vapor to solid state on the multiple packing
of a cooled packed bed is considered. It has been assumed that the coolant used during the
cooling cycle (nitrogen at cryogenic condition) exits in vapor phase and occupies the void space
of the packed bed when the flow of carbon dioxide is introduced.
During the cooling cycle, the entire packed bed is first cooled by sending an inert coolant
(preferably liquid N2) through the packed bed. It is evident that the temperature at the point of
entry of this coolant has the lowest temperature. The exit point of this coolant has the highest
temperature (which is still sufficiently low). During the cooling and capture cycle, the CO2
stream is sent through the packed column in a counter-current manner. The hot CO2 gas stream
enters the packed column at the point where the coolant leaves the packed bed. Thus the hot gas,
as it passes through the packed column it faces lower packing temperature.
There exists different regime of operation inside the packed bed namely cooling section,
capture/deposition section and regeneration section. The incoming hot gas at around ambient
temperature (20-30oC) exchanges the energy with the cooled packing and gets cooled down
inside the first part of the packed column near the upstream section. The temperature of the
packed bed is not low enough to facilitate the deposition of CO2 frost. No frost deposition occurs
in cooling section as the saturation pressure (psat) on the surface of the packing is greater than the
ambient bulk pressure and there exists no net driving force. This section is termed as the cooling
section. As the temperature of the bulk gas decreases and packing temperature increases the gas
stream becomes supersaturated and desublimation of CO2 starts. The desublimation continues as
long as the driving force exists i.e. the bulk pressure remains higher that the saturation vapor
pressure of the solid. Depending on the operating condition the sign of this deviation/ driving
force differs and subsequent sublimation/ regeneration start.

50

3.5.1

Modeling

of

Desublimation

of

Carbon

dioxide

inside

the

Capture/Deposition Zone of the Packed Column


When the packing temperature is sufficiently low (below the desublimation temperature of CO2
at the specified pressure), there is just enough driving force for the frost deposition to occur. The
phenomenon can be described by performing mass and heat balance along the length of the
packed column.
The overall mass balance equation for the gas phase is as follows
t

( g g A p )
t

(m g )
z

( t ) dt
nA p ( t );

mg
z
;

g g Ap

(14)

m g is the total mass flow rate of gas at any axial position, z. The expression in the right hand

side of the equation denotes rate of mass deposition from bulk phase on to the packing of number
density n (number per unit volume of packed bed) (refer to equation (5)).

g , the gas phase void fraction varies with time and axial position
= 1

4 ( + )
2

(15)

, the local velocity of gas inside the packed bed, varies with z due to variation of both m g and
g (due to frost layer deposition). For pure carbon dioxide gas, CO2 the mass fraction of CO2
remains 1. In case of binary mixture of carbon dioxide and methane, carbon dioxide selectively
desublimates and the composition of both the constituents varies along the axial position of the
packed bed. The component mass balance is given by the following equation (16).
( CO 2 g g A p )
t

( CO 2 m g )
z

nA p

CO2

( g D eff
); CO2 CH 4 1 .
z
z

(16)

Considering that the timescale of deposition and growth of the frost layer is large compared to
the mean residence time of the gas, the first unsteady term of equations (14) and (16) are
neglected and pseudo steady state reduced equations are solved.
The energy balance equation for the gas phase is as follows

51

(m g C p gTg )
Tg

( g g C pg )
nA p ( t ) UPerim (T o T g )
(k
);
t
z
z
z
t

( t ) dt

(17)

The first term of the right hand side of the equation denotes the convective heat transfer to the
packing and the second term represents the heat transport from outside ambient atmosphere to
the gas phase due to a very high driving force. Under adiabatic condition (for perfect insulation)
this term may be considered to be negligible. Pseudo steady state assumption allows one to
neglect the unsteady term (1st term of LHS) and to solve the reduced order ODE along with
equation (7).

3.6

Solution Technique

For single packing model, simulations were carried out using the MATLAB 2009b software.
Due to the high stiffness ratio of the above set of ODEs it is required to be solved by the
GEARS Algorithm. MATLAB library function ode15s has been adopted for simulation, which
have GEARs Algorithm inbuilt in it. Equations (5) to (9) are solved to simulate the frost layer
thickness, interface temperature and packing temperature with time.
For the packed bed the overall mass and energy balance equations (14 17) coupled with single
packing equations (5 9) are solved, using pseudo steady state assumptions. A schematic
representation of the numerical grid generation for this moving front problem is shown in Figure
3.2. Along the axial direction over the z, the residence time of the gas varies (increases) due
to mass deposition and variation of g .
For the ease of simulation z is considered to be equal to the packing diameter. Over each z,
, the rate of deposition and the rate of convective heat transfer are evaluated solving

equation (5-9) over the time , the corresponding residence time of the gas within that layer.
Using these values, equations (19-22) are solved to obtain the gas phase temperature (Tg), void
fraction ( g ) and total mass flow rate ( m g ). This two step approach allows one to solve ordinary

52

differential equations rather than full order partial differential equations. For the gas phase the
axial dispersion and conduction of species and energy, respectively are neglected.

Figure 13: Schematic Diagram explaining the Algorithm

53

CHAPTER
4
RESULTS & DISCUSSION

54

4.0 Desublimation kinetics of Carbon dioxide on a single


packing from gas stream
The desublimation kinetics of carbon dioxide on a cryogenically cooled packing from a
relatively hot gas stream was investigated. A base case study simulation was performed with
100% carbon dioxide composition as feed gas. Other simulation variables and parameters of
the base case study are listed in Appendix I. The main reason behind taking pure carbon
dioxide as the base case study is to avoid complication and to check whether the model
replicates the theoretically predicted output in the simulation results.

Since, the main intention is to deal with high carbon dioxide concentration gases,
simulations were also carried out at 70% carbon dioxide concentration. Effects of different
variables like flowrate, initial packing temperature were studied. Variation of a) Frost layer
thickness, b) Rate of deposition, c) Particle Temperature and d) Interfacial Temperature were
recorded with respect to cycle time. In this case only Capture Cycle has been considered.

The details discussion on the simulation results of both base case study and other
simulations is presented in the following section.

4.1 Results of simulation with pure carbon dioxide feed gas


stream
Simulations were carried out with pure carbon dioxide as feed which is the base case study.
Effect of flowrate on variation of a) Frost layer thickness, b) Rate of deposition, c) Particle
Temperature and d) Interfacial Temperature with respect to time has been studied. The
results are presented below.

55

4.1.1 Variation of frost layer thickness () with time at different inlet


gas flowrate

Fig. 14: Effect of inlet gas flow rate on carbon dioxide frost layer thickness ()

Figure 14 shows the variation of frost layer thickness desublimated from 100% CO2 feed stream
on the packing over the cycle time at different inlet gas flow rate. It is observed that the frost
layer increases with the increase in inlet gas flow rate. This happens because the change in
flowrate changes the Reynolds number which in turn changes the heat transfer co-efficient and
mass transfer co-efficient. As the result the transport phenomena is affected which affects the
thickness of the frost layer deposited.

56

4.1.2 Rate of frost layer deposition with time at different inlet gas
flowrate

Fig. 15: Effect of inlet gas flow rate on rate of deposition of carbon dioxide frost layer

Figure 15 shows the variation of rate of deposition of carbon dioxide frost layer on the packing
over the cycle time at different inlet gas flow rate. The maximum rate of deposition is observed
at 10 lpm inlet flowrate but the rate sustained longer at 2 lpm which is the minimum flowrate.
This variation is due to the variation of residence time at different flow rates that varies antiproportionately as well the Sherwood number of the system changes which dictates the transport
phenomena of system. That is why for the maximum flowrate a sharp peak for rate change of
deposition is obtained.

57

4.1.3 Rate of change of frost layer thickness with time at different


inlet gas flowrate

Fig. 16: Effect of inlet gas flow rate on rate of change of carbon dioxide frost layer

Figure 16 shows the variation of rate of change of frost layer thickness over the cycle time at
different inlet gas flow rate. It can be observed that, at higher flow rate, the rate of change of
frost layer thickness is high and reaches to saturation faster. The explanation is same as the Fig.
15. Another approach of explaining the reason behind this is that, at higher flow rate the
Reynolds number of the system increases which leads higher mass transfer coefficient.

58

4.1.4 Variation of Interface Temperature with time at different inlet


gas flowrate

Fig. 17: Effect of inlet gas flow rate on Interfacial Temperature (Ti)

Figure 17 shows the effect inlet gas flow rate on the interfacial temperature. With the increasing
inlet feed gas flowrate the Reynolds number increases leading to a higher heat transfer coefficient. Also the residence time of the gas decreases with increase in feed gas flowrate. The
variation of temperature in the curve is due to these reasons. However, the cold duty remains the
same since the bulk pressure remains constant resulting into constant interfacial temperature in
all three cases.

59

4.2 Results of simulation with carbon dioxide and methane


mixture as feed gas stream
Simulations were carried out with a gas mixture of 70% carbon dioxide and 30% methane as
feed gas stream. Effect of different parameters on variation of a) Frost layer thickness, b) Rate
of deposition, c) Rate of change of frost layer thickness, d) Particle Temperature and e)
Interfacial Temperature with respect to time has been studied.

4.2.1 Variation of frost layer thickness () with time at different bulk


pressure

Fig. 18: Effect of bulk pressure on frost layer thickness with time

Figure 18 shows the variation of frost layer thickness with time for different bulk pressure. It can
be observed that with increasing the bulk pressure, the frost layer thickness increases. This is
because with increasing bulk pressure, the driving force for mass deposition increases resulting
in increased frost deposited with time.

60

4.2.2 Rate of change of frost layer deposition with time at different


inlet gas flowrate

Fig. 19: Effect of inlet gas flow rate on rate of deposition of frost layer thickness

Figure 19 shows the variation of rate of deposition of frost layer over the cycle time at different
inlet gas flow rate. It can be observed that, at higher flow rate, the rate of change of frost layer
thickness is high and reaches to saturation faster. The explanation is same as the Fig. 15.
Compared to Figure 15 the magnitude of rate of deposition is lower. This is mainly because of
the change is CO2 concentration which decreases the bulk pressure.

61

4.2.3 Variation of Particle Temperature with time at different bulk


pressure

Fig. 20: Effect of bulk pressure on Particle Temperature (Tp)

Figure 20 shows the effect of bulk pressure on the particle temperature (Tp). It is observed that at
higher pressure particle temperature is higher. While increasing the pressure, both the frost layer
thickness as well as the rate of frost deposition increases due to increased driving force which
enhances the mass transfer phenomena. It results in higher requirement for cold duty. As a result,
more increase in particle temperature at higher pressure takes place.

62

4.2.4 Variation of Interface Temperature with time at different inlet


gas flowrate

Fig. 21: Effect of inlet gas flow rate on Interfacial Temperature (Ti)

Figure 21 shows the effect of inlet gas flowrate on the interfacial temperature (Tp). Compared to
figure 17 the interfacial temperature has decreased by almost 15K. The main reason is, due to
desublimation of carbon dioxide the bulk pressure decreases which alters the driving force.

63

4.3 Effect variation of CO2 percentage on Frost Layer


Thickness

Fig. 22: Effect of variation of carbon dioxide in feed gas stream on frost layer thickness

Figure 22 shows the effect of variation of concentration of carbon dioxide in the feed gas stream
on the frost layer thickness. It can be observed, as the concentration of CO2 in the feed gas
mixture reduces, CO2 frost layer thickness decreases. This is because, with decreased CO2
percentage, the driving force for CO2 mass deposition decreases. So, at 90% CO2 concentration
the frost layer is maximum.

64

4.4 Effect of CO2 composition on Particle Temperature

Fig. 23: Effect of variation of carbon dioxide in feed gas stream on Particle Temperature (Tp)

Figure 23 shows the effect of variation of CO2 in the feed gas stream with dimensionless time
(t*). It is seen that, as the percentage CO2 in the feed mixture increases, it leads to higher particle
temperature as the cold duty requires for desublimation of CO2 increases with increasing amount
of CO2. As a result the particle temperature increases more with increase in CO2 percentage in
the feed.

65

4.5 Dynamics of CO2 capture inside a cryogenically cooled


packed bed with pure CO2 as feed.
The dynamics inside a cryogenically cooled packed bed has been studied with pure CO2 at
different temperature profile, feed flowrate and flow arrangement. The parameter and variable
list of the base case is listed in Appendix I. The results have been discussed below.

4.5.1 Variation of frost layer thickness with time at different position


along the bed for co current flow

Fig. 24: Growth of CO2 frost with time at different axial position of the bed for
Co current flow at 5 lpm inlet gas flowrate and Temperature Profile 3

From figure 24, it is observed that the frost layer thickness becomes maximum in the beginning
and least at the end. Since this is a case of the co-current flow configuration, the lowest
temperature at the inlet provides maximum driving force which leads to highest frost layer
thickness in the beginning. As the gas travels along the bed the driving force reduces and gives
least frost layer at the end.

66

4.5.2 Variation of frost layer thickness with time at different position


along the bed for counter current flow

Fig. 25: Growth of CO2 frost with time at different axial position of the bed for
Counter current flow at 5 lpm inlet gas flowrate and Temperature Profile 3

Figure 25 shows the growth of CO2 frost with time at different axial position of the bed for
Counter current flow at 5 lpm inlet gas flowrate and Temperature Profile 3. It can be seen that
the frost layer thickness is increasing with axial position and is maximum at 27cm. Thereafter, it
starts decreasing again. Due to counter current flow configuration is it expected to have
maximum frost layer at the end of the bed. But due to low inlet pressure, desublimation on
initial bed position lowers the overall bulk pressure which then affects the mass transfer coefficient.

67

4.5.3 Contour plot of frost layer thickness with time and axial position
for co current flow

Fig. 26: Contour plot of CO2 frost vs. time vs. Axial position for
Co current flow at 5 lpm inlet gas flowrate and Temperature Profile 3

Figure 26 shows a contour plot of frost layer thickness with respect to time and axial distance for
co-current flow. As seen before, the frost layer is maximum in the initial zone and there after it
decreases. It is also observed that within the region of axial distance 0.10 to 0.25 the variation is
maximum. This is due to the highest driving force in the inlet.

68

4.5.4 Contour plot of frost layer thickness with time and axial position
for counter current flow
5lpm, Temperature Profile 1

Fig. 27: Contour plot of CO2 frost vs. time vs. Axial position for
Counter current flow at 5 lpm inlet gas flowrate and Temperature Profile 1

Figure 27 shows a contour plot of frost layer thickness with respect to time and axial distance for
counter current flow. In this case it is clear that the maximum frost deposition is towards the end
of the bed, which is ought to happen in the case of a counter current flow. Also the time of this
maximum growth is the last half of the total capture cycle.

69

10 lpm, Temperature Profile 3

Fig. 28: Contour plot of CO2 frost vs. time vs. Axial position for
Counter current flow at 10 lpm inlet gas flowrate and Temperature Profile 3

Figure 28 shows a contour plot of frost layer thickness with respect to time and axial distance for
counter current flow. Here the gas flow rate is 10lpm and also the bed temperature profile is 3. In
this case also, the maximum frost deposition is towards the end of the bed and the frost layer
thickness is higher. This is due to the increased mass transfer enhanced by the higher feed
flowrate. Also the temperature profile plays a vital role in it.

70

4.5.5 Surface plot of frost layer thickness with time and axial position for
counter current flow

Fig. 29: Surface plot of CO2 frost vs. time vs. Axial position for
Counter current flow at 5 lpm inlet gas flowrate and Temperature Profile 3

The surface plot (Fig. 29) of carbon dioxide frost vs. time vs. axial distance gives the idea of
variation frost layer with time and axial position. This plot is for counter current flow. It also
conforms to the behavior of frost layer thickness as found in the previous cases.

71

4.5.6 Growth of frost layer thickness with time and axial position for
counter current flow

Fig. 30: Growth of CO2 frost with time at different axial position of the for
Counter current flow at 10 lpm inlet gas flowrate and Temperature Profile 3

Figure 30 shows the growth of carbon dioxide frost layer thickness with time at different axial
position for counter current flow. Maximum frost deposition was found to be at axial position of
27 cm.

72

4.5.7 Variation of outlet mass flowrate thickness with time and axial
position for counter current flow

Fig. 31: Variation of outlet Mass flowrate with time at different axial position of the for
Counter current flow at 10 lpm inlet gas flowrate and Temperature Profile 3

Figure 33 shows the variation of mass flowrate with time at different axial position for counter
current flow. It is observed that the mass flowrate increased with time. At the end of each curve a
patch is observed which accounts to some lower data points. Actually at that time in those
position rapid desublimation and sublimation was occurring simultaneously. That is the reason
for such a nature of the curve.

73

4.5.8 Surface Plot of frost layer thickness with time and axial position
for counter current flow

Fig. 32: Surface plot of outlet mass flowrate vs. time vs. Axial position for
Counter current flow at 10 lpm inlet gas flowrate and Temperature Profile 2

Figure 34 shows the surface plot of mass flowrate vs. time vs. axial position for counter current
flow. It is observed that the mass flowrate increases with time at the outlet, whereas; the flowrate
is maximum at the inlet position, and decays along the bed length.

74

4.5.9 Percentage separation of carbon dioxide of with axial position at


different time for counter current flow

(cm)

Fig. 33: Percentage separation of CO2 frost vs. Axial position at different time for
Counter current flow at 5 lpm inlet gas flowrate and Temperature Profile 3

The percentage separation of carbon dioxide is the ultimatum in this study. Percentage separation
of carbon dioxide was plotted against axial distance at different time (Fig. 33). It can be observed
that in most of the cases the 100% separation is obtained which is good for the purpose.

75

4.5.10 Contour plot of percentage separation of carbon dioxide with time


and axial position for counter current flow

Fig. 34: Contour plot of percentage separation of CO2 vs. time vs. Axial position for
Counter current flow at 5 lpm inlet gas flowrate and Temperature Profile 3

The contour plot of percentage separation shows that maximum separation is obtained within the
axial distance of 20 cm to 45 cm. The time span of 0 to 225 seconds is best suitable for
maximum separation of carbon dioxide.

76

4.5.11 Contour plot of frost layer deposition on only packing surface


(heterogeneous nucleation) with time and axial position for counter
current flow
The deposition of carbon dioxide frost occurs both on packing as well as the bed wall. An
attempt has been taken to find the deposition on wall and packing separately.

Fig. 35: Contour plot of deposition of CO2 frost on packing vs. time vs. Axial position for
Counter current flow at 5 lpm inlet gas flowrate and Temperature Profile 3

Figure 35 shows the contour plot of deposition of carbon dioxide frost on the cooled packing
only. The process can be described using the heterogeneous nucleation. It shows that, maximum
deposition on the packing occurs towards the end of the packed bed. It is also observed that the
deposition is more of less constant throughout the cycle in the last half of the bed.

77

4.5.11 Surface plot of frost layer deposition on only packing surface


(heterogeneous nucleation) with time and axial position for counter
current flow

Fig. 36: Surface plot of deposition of CO2 frost on packing vs. time vs. Axial position for
Counter current flow at 5 lpm inlet gas flowrate and Temperature Profile 3

The surface plot of the same (Fig. 36) shows that the deposition on packing increases with time
and after 15 cm distance, it is almost constant for a particular axial position. The deposition on
the packing increases with axial distance and is maximum at the tail end of the bed.

78

4.5.12 Contour plot of frost layer deposition on only bed wall


(heterogeneous nucleation) with time and axial position for counter
current flow

Fig. 37: Contour plot of deposition of CO2 frost on bed wall vs. time vs. Axial position for
Counter current flow at 5 lpm inlet gas flowrate and Temperature Profile 3

Figure 37 shows the contour plot of deposition of carbon dioxide frost on the packed bed walls
only. The process can be described using the heterogeneous nucleation.

In this case also,

maximum deposition on the packing occurs towards the end of the packed bed. It is also
observed that the deposition is very during more than 60% time of the capture cycle in the first
half of the packed bed.

79

4.5.13 Surface plot of frost layer deposition on only bed wall


(heterogeneous nucleation) with time and axial position for counter
current flow

Fig. 38: Surface plot of deposition of CO2 frost on bed wall vs. time vs. Axial position for
Counter current flow at 5 lpm inlet gas flowrate and Temperature Profile 3

The surface plot (Fig. 38) of the deposition on the bed wall conforms to the result of the contour
plot. The deposition increases with axial distance and the deposition is very less during almost
60% time of the capture cycle. It increases swiftly towards the last section.

80

4.5.14 Effect of homogeneous nucleation on saturation time during the


capture cycle

Fig. 39: Effect of Homogeneous Nucleation on the saturation time for the capture cycle for
Counter current flow at 5 lpm inlet gas flowrate and Temperature Profile 3

The effect of consideration of homogeneous nucleation for frost formation inside the packed bed
void space is given in figure 39. It is observed that considering the homogeneous nucleation
increases the saturation time from 82.47 to 92.03 seconds. Though, not always homogeneous
nucleation will occur due to its high Gibbs free energy of formation, however if it happens it will
be beneficial for the process.

81

4.5.15 Effect of inlet gas feed flowrate on bed saturation time during the
capture cycle

Fig. 40: Effect of inlet gas feed flowrate on the saturation time for the capture cycle for
Counter current flow at 5 lpm inlet gas flowrate and Temperature Profile 3

Figure 40 depicts the effect of inlet feed flowrate on the saturation time for the capture cycle in a
counter current flow arrangement. It can be observed that the flowrate of 2 lpm gives the
maximum saturation time whereas 10 lpm gives the least time. This is mainly due to the
increased residence time for the lower feed flowrate.

82

4.6 Dynamics of CO2 capture inside a cryogenically cooled


packed bed with 80% CO2 as feed
Simulations were executed with inlet feed gas concentration of 80% Carbon dioxide and rest
methane. Some of the results are given below.

4.6.1 Variation of frost layer thickness with time at different position


along the bed for counter current flow

Fig. 41: Growth of CO2 frost with time at different axial position of the bed for
Counter current flow at 5 lpm inlet gas flowrate and Temperature Profile 3

Figure 41 represents the growth of frost with time at different axial position of the bed for
Counter current flow. It is observed that maximum frost layer is at axial position 18 cm.

83

4.6.2 Variation of normalized mass flow with axial distance at different


time for 80% CO2 composition in feed gas mixture and
countercurrent flow

Fig. 42: Variation of normalized mass flow with axial distance at different time for
Counter current flow at 5 lpm inlet gas flowrate and Temperature Profile 3

Figure 42 represents the Variation of normalized mass flow with axial distance at different time
for Counter current flow. In the beginning the mass flow is max and it diminished with axial
distance. However, at t=100s the mass flow increases at the end of the bed due to sublimation of
previous frost layers.

84

4.7 Validation of simulation results with experimental


results
The results obtained from the simulation study were compared with the available experimental
results from literature of Abulhassan et al.(2014), the team working at the Universiti of
Teknologi, PETRONAS.

Fig. 43: Comparison of simulation and experimental results of variation of percentage CO2 with
time at different bed temperature profiles for Counter current flow at 5 lpm gas flowrate.

Figure 43 shows the comparison of simulation and experimental results. It shows that the simulations
results are in good compliance to the experimental results. The trends of the curves are also similar.
Hence, validation of the simulation results with experimental results makes the model realistic.

85

CHAPTER
5
CONCLUSION

86

5.0 Conclusion
In this study, a cryogenically cooled packed bed has been modeled. .A two step model has been
considered that takes into account the diffusion from supersaturated gas phase to the gas solid
interface and relatively slower crystallization kinetics and nucleation on a heterogeneous surface
(packing) in series. This has been used to simulate the kinetics and growth rate of carbon dioxide
deposition on a single packing from pure and mixed carbon dioxide gas stream. Thereafter the
single packing model has been embedded into another model that is of the total packed bed.
Frost layer thickness, Interfacial temperature, Packing Temperature, Rate of Frost deposition and
rate of change of frost layer thickness has been investigated by executing simulations in
MATLAB.

The variations of these have been monitored at different operating conditions.

Increase in pressure and decrease in initial packing temperature increases the rate of deposition
of CO2 frost.

The performance of a total packed bed consisting of multiple packing is simulated by using a
model where pseudo steady state gas phase balance equations are solved along with the single
packing unsteady model. The results shows that higher deposition occurs for counter current
flow arrangement than the co-current flow, which means percentage separation of CO2 is more in
case of counter current arrangement. For co-current flow the thickness of the frost layer is the
maximum near the inlet section whereas for counter current flow arrangement the frost layer
thickness is the maximum near the downstream, where the temperature is the lowest. Hence, the
chances of choking are more in the outlet zone for counter current flow. Co-current flow has the
tendency to choke the packed bed near the inlet section. The simulated results were also
compared with the experimental results and it was found that the results of the simulation are in
good compliance to the experimental data, which validates the model to be valid in the real case.

The saturation time of the packed bed signifies the maximum cycle time of CO2 capture by
desublimation and frost formation inside the packed bed. Increase in inlet gas flow rate decreases
the saturation time. Simulation of frost layer growth kinetics and saturation time is of
significance for bed switching. The significance of the study is in design and optimization of
cryogenic separation of carbon dioxide from flue gas and natural gas.

87

5.1 Future Scope


There exists a lot of potential for future investigations of this work. Some of them are listed
below.
Further investigation can be done to check the robustness of the model by changing
parameters and operation conditions.
The model can be validated with ternary gas mixtures.
Optimization of the system can be done.
Sensitivity Analysis can be carried out.
LCA and Techno-economic analysis can be done.
Hydrate Formation can be predicted etc.

88

REFERENCES

89

[1]

Abulhassan A, Ganguly S, Shariff ABM. Simulation of cryogenic packed bed using 1dimensional pseudo homogeneous model. Journal of Applied Sciences 15 (3): 492
499, 2015

[2]

Abulhassan A, Syahera MN, Maqsood K, Ganguly S. Minimization of energy


requirements using nonconventional cryogenic separation. International Journal of
Applied Engineering Research, Submitted 2014.

[3]

Al-Juaied, M. A. (May 2004). Carbon dioxide removal from natural gas by membranes
in thepresence of heavy hydrocarbons and by Aqueous Diglycolamine/Morpholine,
PhD thesis, pp. 1-424, The University of Texas at Austin, Texas.

[4]

An, H., Feng, B., Su, S., (2011). CO2 capture by electrothermal swing adsorption with
activated carbon fibre materials. Int.J. Greenh.Gas Con.5,1625.

[5]

Atkinson TD, Lavin JT, Linnett DT. (1988). 4,759,786. US Patent.

[6]

Arai Y, Kaminishi G-I, Saito S. The experimental determination of the P-V-T-X


relations for the carbon dioxide-nitrogen and the carbon dioxide-methane system. J
Chem Eng Jpn 1971; 4: 113 122.

[7]

Aliredza M. Multiple cryogenic packed bed dehydration and separation of CO2 from
natural gas. BTech Project Report, Universiti Teknologi PETRONAS, 2013.

[8]

Al-Sahhaf TA, Kidnay AJ, Sloan ED. Liquid + vapor equilibriums in the nitrogen +
carbon dioxide + methane system. Ind Eng Chem Fundam 1983; 22: 372 380.

[9]

Al-Sahhaf TA. Vapor-liquid equilibria for the ternary system N2 + CO2 + CH4 at 230
and 250 K. Fluid Phase Equilib 1990; 55:159 172.

90

[10]

Baker, R. W. (2004). Membrane Technology and Applications (2nd edition), John Wiley
& Sons, ISBN 0-470-85445-6, West Sussex

[11]

Berstad D, Neks P, Anantharaman R. Low-temperature CO2 Removal from Natural


Gas. Energy Procedia 2012; 26(0): 41-48.

[12]

David Berstad, Rahul Anantharaman, Petter Neksa, Low-temperature CO2 capture


technologies Applications and potential, international journal of refrigeration 36 (2013)
1403 - 1416.

[13]

Binay K Dutta (2007), Principles of Mass Transfer and Separation Processes, PHI India.
ISBN-10: 8120329902

[14]

Biruh Shimekit and Hilmi Mukhtar (2012). Natural Gas Purification Technologies Major Advances for CO2 Separation and Future Directions, Advances in Natural Gas
Technology, Dr. Hamid Al-Megren (Ed.), ISBN: 978-953-51-0507-7, In Tech,
Available

from:

http://www.intechopen.com/books/advances-in-natural-

gastechnology/natural-gas-purification-technologies-major-advances-for-co2-separationand-future-directions
[15]

BP Energy Outlook 2035, January 2014 Available from: bp.com/energyoutlook

[16]

Christopher H, Maarten V D B. (2008). In: Gasification 2nd Edition. Amsterdam:


Elsevier. 330.

[17]

Clodic, D. and M. Younes (2002). Method and system for recovery of carbon dioxide
from flue gases by desublimation for its storage, Armines, Fr. . 64 pp.

91

[18]

Clodic D, Younes M. A new Method for CO2 Capture: Frosting CO2 at Atmospheric
Pressure. In J. Gale & Y. Kaya (Eds.), Greenhouse Gas Control Technologies - 6th
International Conference 2003 (pp. 155-160). Oxford: Pergamon.

[19]

Clodic D, El Hitti R, Younes M, Bill A, Casier F. CO2 capture by anti-sublimation

[20]

Thermo-economic process evaluation. Paper presented at the Fourth Annual Conference


on Carbon Capture & Sequestration 2005, Alexandria, USA.

[21]

Clodic D, Younes M. Method of extracting carbon dioxide and sulphur dioxide by


means of anti-sublimation for Storage thereof. US 2006/0277942 A1.

[22]

Clodic D, Younes M. Method and system for extracting carbon dioxide by antisublimation for Storage thereof. US 7,073,348 B2, 2006.

[23]

Christian. J.W., The Theory of Transformations in Metals and Alloys, Part I:


Equilibrium and General Kinetic Theory, Pergamon Press, p. 432, 1975.

[24]

Darman NH, Harum ARB. Technical Challenges and solutions on Natural Gas
Development in Malaysia. Paper presented at the The petroleum Policy and
Management Project, 4th Workshop of the China-Sichuan Basin Study 2006, Beijing,
China.

[25]

Davis JA, Rodewald N, Kurata F. Solid-liquid-vapor phase behavior of the methane


carbondioxide system. AlChE J 1962; 8(4): 537-539.

[26]

Davalos J, Anderson WR, Phelps RE, Kidnay AJ. Liquid-vapor equilibria at 250.00.
deg. K for systems containing methane, ethane, and carbon dioxide. J Chem Eng Data
1976; 21: 81 84.

92

[27]

Donnelly HG, Katz DL. Phase Equilibria in the Carbon DioxideMethane System. Ind
Eng Chem 1954; 46(3): 511-517.

[28]

Eggeman et. al. Pitfalls Of CO2 Freezing Prediction Presented at the 82nd Annual
Convention of the Gas Processors Association San Antonio, Texas, March 10, 2003

[29]

Ely JF, Haynes WM, Bain BC. Isochoric (p, Vm, T) measurements on CO2 and on
(0.982 CO2 + 0.018 N2 ) from 250 to 330 K at pressures to 35 MPa. J Chem Thermodyn
1989; 21: 879 894.

[30]

ExxonMobil, The Outlook for Energy, A view to 2020; 2015

[31]

Eric Favre , Bouchra Belaissaoui , Yann Le Moullec , David Willson , Hybrid


membrane cryogenicprocess for post-combustion CO2 capture, Journal of Membrane
Science 415416 (2012) 424434.

[32]

Glassccok, D. A. (1990). Modeling and experimental study of carbon dioxide absorption


into aqueous alkanolamines, PhD thesis, pp. (1-292), The University of Texas at Austin,
Texas.

[33]

Grande, C.A., Rodrigues, A., (2008). Electric swing adsorption for CO2 removal from
flue gases. Int.J. Greenh.Gas Con. 2,194202.

[34]

Gunn, D.J., 1978, Transfer of heat or mass to particles in fixed and fluidized beds.
International Journal of Heat and Mass Transfer 21 (4), 467476.

[35]

Hao, G.-P., Li,W.-C., Lu,A.-H., (2011). Novel porous solids for CO2 capture. J.Mater.
Chem. 21,64476451.

[36]

Hart, A., N. Gnanendran, (2009), Cryogenic CO2 capture in natural gas, Energy
Proceedia, 1, 697-706.

93

[37]

Guang-Yan Zhu, Michel A. Henson, Lawrence Megan, Low-order dynamic modeling


of cryogenic distillation columns based on nonlinear wave phenomenon, Separation
and Purification Technology 24 (2001) 467487

[38]

Holmes, A.S. and J. M. Ryan, (1982). Cryogenic Distillative Separation of Acid Gases
from Methane.

[39]

Holmes, A.S., B. C. Price, J. M. Ryan, and R. E. Styring, (1983). Pilot tests prove out
cryogenic acid-gas/hydrocarbon separation processes, Oil Gas J, vol. 81, 85-86.

[40]

Hubbard, B., 2010. New and Emerging Technologies (Petroskills workshop). 2010 Gas
Processors Association Convention. John M. Campbell & Co, Austin, Texas

[41]

Hwang S-C, Lin H-M, Chappelear PS, Kobayashi R. Dew point study in the vaporliquid region of the methane-carbon dioxide system. J Chem Eng Data 1976; 21: 493
497.

[42]

International Energy Agency (IEA), Key World Energy Statistics; 2014

[43]

Karen HWW. Cryogenic multiple bed dehydration and CO2 separation during
purification of natural gas. B Tech Project Report, Universiti Teknologi PETRONAS,
2013.

[44]

Kaminishi G-I, Arai Y, Saito S, Maeda S. Vapor-liquid equilibria for binary and ternary
systems containing carbon dioxide. J Chem Eng Jpn 1968; 1: 109 116.

[45]

Kidnay. A.J., Parrish, W. (2006). Fundamentals of Natural Gas Processing. CRC Press,
Boca Raton.

[46]

Kohl, A. L. and R. B. Nielsen (1997). Gas Purification (5th edition), Gulf Professional
Publishing, ISBN 978-0-8841-5220-0, Texas

94

[47]

Kerry, F. G. (2007). Industrial Gas Handbook: Gas Separation and Purification, CRC,
ISBN 978-0-8493-9005-0, New York

[48]

Liu K, Song C, Subramani V.

(2009) In: Hydrogen and Syngas Production and

Purification Technologies. New Jersey: John Wiley and Sons, 275.


[49]

X. Y. Liu, and N. Du, Zero-sized effect of nano-particles and inverse homogeneous


nucleation, Journal of biological Chemistry, Vol. 279, No. 7, pp. 6124-6131, 2004

[50]

Larikov D D, Oyama S T. (2011). In: Review of CO2/CH4 Separation Membranes.

[51]

Ma. J, Heterogeneous nucleation on convex and concave spherical surfaces, PhD.


Thesis, University of Portsmouth, Portsmouth, England, 2008.

[52]

Maqsood K, Pal J, Turunawarasu D, Pal AJ, Ganguly S. Performance enhancement and


energy reduction using Hybrid Cryogenic Distillation Networks for purification of
natural gas with high CO2 Content. Korean J Chem Eng. 2014, 31 (7), 11201135. DOI:
10.1007/s11814-014-0038-2014

[53]

Maqsood K, Ali A, Shariff A.B.M., Ganguly S; Synthesis of Conventional and Hybrid


Cryogenic Distillation Sequence for Purification of gas. Journal of Applied Sciences,
2014

[54]

Maqsood K, Ali A, Shariff A.B.M., Ganguly S; Techno-economic evaluation of


Cryogenic Networks for separation of CO2 from natural gas. Applied Mechanics and
Materials, Vol. 625, pp. 635 638, 2014

[55]

Maqsood K, Shariff A.B.M., Ganguly S; Synthesis of Energy Efficient Cryogenic


Distillation Networks for Maximum Methane Recovery from Natural Gas with Carbon
Dioxide and Heavy Hydrocarbons. Journal of Applied Sciences 15 (3): 492 499, 2015

95

[56]

Magee JW, Ely JF. Isochoric (p, v, T) measurements on CO2 and (0.98 CO2 + 0.02 CH4
) from 225 to 400 K and pressures to 35 MPa. Int J Thermophys 1988; 9: 547 557.

[57]

Meyers, R. A. (2001). Chemical Engineering. Encyclopedia of Physical Science and


Technology (3rd edition), Ramtech, Inc. California.

[58]

Mersmann, A., M. Kind, et al. (2011). Thermal Separation Technology Principles,


Methods, Process Design, Springer, ISBN 978-3-642-12524-9, New York

[59]

R. MAHAJAN, W. J. KOROS, Factors controlling sucessful formation of mixed-matrix


gas separation membranes, Ind. Eng. Chem Res. 39 (2000) 2692.

[60]

Mraw SC, Hwang S-C, Kobayashi R. Vapor-liquid equilibrium of the methane-carbon


dioxide system at low temperatures. J Chem Eng Data 1978; 23: 135 139.

[61]

Mukhopadhyay Mamata (2010), Fundamentals of Cryogenic Engineering, ISBN 97881-203-3057-3, PHI Learning Private Limited, New Delhi.

[62]

Mullick A. Transport phenomena modeling and simulation of novel dynamic bed for
carbon capture. M.E Thesis, Jadavpur University, Kolkata, 2014

[63]

NaturalGas.org. (2010). Overview of Natural Gas, In: Background, 22.06.11, Available


from: http://www.naturalgas.org/overview/background.asp

[64]

Neumann P, Walch W. dampf/flussigkeits-gleichgewicht CH4 -CO2in bereich tiefer


temperaturen und kleiner CO2 -molenbruche. Chem Ind Technol 1968; 40: 241 244.

[65]

Nielson, Bradley J., "Cryogenic Carbon Capture using a Desublimating Spray Tower"
(2013). All Theses and Dissertations. Paper 3721.

96

[66]

Northrop, P.S., J.A. Valencia, (2009) The CFZ Process: A Cryogenic method for
handling high-CO2 and H2S gas reserves and facilitating geo sequestration of CO2 and
acid gases, Energy Procedia, 1, 171-177.

[67]

S. P. Nunes and K.-V. Peinemann (2001), Membrane Technology in the Chemical


Industry. First Edition. Wiley-VCH Verlag GmbH ISBN: 3-527-60038-8

[68]

Neumann P, Walch W. dampf/flussigkeits-gleichgewicht CH4 -CO2in bereich tiefer


temperaturen und kleiner CO2 -molenbruche. Chem Ind Technol 1968; 40: 241 244.

[69]

Natural

Gas

Consumption

in

the

world.

Available

from:

https://yearbook.enerdata.net/natural-gas-consumption-in-the-world.html Last viewed on


27th May, 2015
[70]

Olajire. A.A (2010). CO2 Capture and Sequestration Technologies for End-of-pipe
Application. Energy, 35, 2610-2628.

[71]

Pikaar MJ. Study of phase equilibria in hydrocarbon-CO2 systems. London: University


of London, 1959

[72]

Perrotin, T. and D. Clodic (2005). CO2 gas cooler modeling and optimization,
International Institute of Refrigeration.

[73]

R. Prasad, R. L. Shanerand, K. J. Doshi. Comparison of membranes with other gas


separation technologies. in: Polymeric gas separation membranes, D. R. PAUL, Y. P.
YAMPOLSKII (Eds.), CRC Press, Boca Raton 1994

97

[74]

Rufford. T. E, Smart. S, Watson G.C.Y, Graham B. F, Boxall. J, Diniz da Costa. J. C,


May. E. F. (2012). The removal of CO2 and N2 from natural gas: A review of
conventional and emerging process technologies. Journal of Petroleum Science and
Engineering 94-95, 123154

[75]

Rajani, J.B., (2004). Treating technologies of shell global solutions for natural gas and
refinery gas streams. In: Research Institue of Petroleum Industry Congress 12 Iran.

[76]

Seader, J.D., Henley, E.J., (2006). Separation Process Principles. John Wiley & Sons,
Hoboken, USA.

[77]

Sear, R. P. (2007), Nucleation: theory and applications to protein solutions and


colloidal suspensions. J.

Physics Cond. Matt. 19 (3): 033101. doi:10.1088/0953-

8984/19/3/033101.
[78]

Shekhawat, D., D. R. Luebke, et al. (2003). A Review of Carbon Dioxide Selective


Membranes: A Topical Report, In: CO2 selective membranes, 13.07.11,Available from:
http://www.osti.gov/bridge/product.biblio.jsp?osti_id=819990

[79]

Sarashina E, Arai Y, Saito S. Vapor-liquid equilibria for the nitrogenmethane- carbon


dioxide system. J Chem Eng Jpn 1971; 4: 377 378.

[80]

Schach, M.-O., B. Oyarzun, H. Schramm, R. Schneider and J.-U. Repke (2011).


Feasibility study of CO2 capture by anti-sublimation." Energy Procedia 4: 1403-1410.

[81]

Seitz JC, Blencoe JG, Bodnar RJ. Volumetric properties for x1 CO2 + x2 CH4 + (1-x1 x2) N2 at the pressures (19.94, 39.94, 59.93, and 99.93) MPa and temperatures (323.15,
373.15, 473.15, and 573.15) K. J Chem Thermodyn 1996; 28: 539 550.

98

[82]

Song, C. F., Y. Kitamura and S. H. Li (2012); "Evaluation of Stirling cooler system for
cryogenic CO2 capture." Applied Energy 98: 491-501

[83]

Song, C. F., Y. Kitamura, S. H. Li and W. Z. Jiang (2012); "Parametric Analysis of a


Novel Cryogenic CO2 Capture System Based on Stirling Coolers." Environmental
Science & Technology 46(22): 12735-12741.

[84]

Song, C. F., Y. Kitamura, S. H. Li and K. Ogasawara (2012); "Design of a cryogenic


CO2 capture system based on Stirling coolers." International Journal of Greenhouse Gas
Control 7: 107-114.

[85]

Song, C. F., Yutaka Kitamura, Weizhong Jiang, Application of Free Piston Stirling
Cooler (SC) on CO2 Capture Process, Energy Procedia 37 ( 2013 ) 1239 1245.

[86]

Song, C. F., Y. Kitamura, S.-H. Li and W.-Z. Jiang (2013); "Analysis of CO2 frost
formation properties in cryogenic capture process" International Journal of Greenhouse
Gas Control 13: 26-33

[87]

Song, C. F., Yutaka Kitamura, Weizhong Jiang, Deposition CO2 Capture Process Using
a Free Piston Stirling Cooler, Ind. Eng. Chem. Res. 2013, 52, 1493614943.

[88]

Song, C. F., Yutaka Kitamura , Shuhong Li, Optimization of a novel cryogenic CO2
capture process by response surface methodology (RSM), Journal of the Taiwan
Institute of Chemical Engineers 45 (2014) 16661676.

[89]

Song, C. F., Yutaka Kitamura , Shuhong Li, Energy analysis of the cryogenic CO2
capture process based on Stirling Coolers, Energy 65 (2014) 580-589.

99

[90]

Song, C. F., Jingwen Lu , Yutaka Kitamura, Study on the COP of free piston Stirling
cooler (FPSC) in the anti-sublimation CO2 capture process, Renewable Energy 74
(2015) 948-954.

[91]

Somait FA, Kidnay AJ. Liquid-vapor equilibriums at 270.00 K for systems containing
nitrogen, methane, and carbon dioxide. J Chem Eng Data 1978; 23: 301 305.

[92]

Burdyny. T, Struchtrup. H, Hybrid membrane/cryogenic separation of oxygen from


air for use in the oxy-fuel process, Energy 35 (2010) 18841897.

[93]

Surovtseva D, Robert Amin1, Ahmed Barifcani, Design and operation of pilot plant for
CO2 capture from IGCC flue gases by combined cryogenic and hydrate method,
chemical engineering research and design 89( 2011 ) 17521757.

[94]

Trappehl G, Knapp H. Vapour-liquid equilibria in the ternary mixtures N2 -CH4 -C2 H6


and N2 -C2 H6 -C3 H8 . Cryogenics 1987; 27: 696 716.

[95]

Tagliabue, M., Farrusseng, D., Valencia, S., Aguado, S., Ravon, U., Rizzo, C., Corma,
A., Mirodatos, C., (2009). Natural gas treating by selective adsorption: material science
and chemical engineering interplay. Chem. Eng. J. 155, 553566.

[96]

Tin P S, Chung T S, Liu Y,Wang R. Carbon, (2004), 42(15): 3123.

[97]

C. TSAI, S. TAM, Y. LU, C. J. BRINKER, Dual layer asymmetric microporous silica


membranes, Journal of Membrane Science 169 (2000) 255.

[98]

Thrasher J, Fleet AJ. (1995). Predicting the Risk of Carbon Dioxide 'Pollution' in
Petroleum Reservoirs, Grimalt. J.O. & Dorronsoro. C, eds., Organic Geochemistry:
Developments and Applications to Energy, Climate, Environment and Human History.

100

Paper presented at the 17th International Meeting on Organic Geochemistry, San


Sebastian, AIGOA.
[99]

Tuinier MJ, van Sint Annaland M, Kramer GJ, Kuipers JAM. Cryogenic CO2 capture
using dynamically operated packed beds. Chem Eng Sci 2010; 65(1): 114-119.

[100]

Tuinier MJ, Hamers HP, van Sint Annaland M. Techno-economic evaluation of


cryogenic CO2 capture A comparison with absorption and membrane technology.
INT J GREENH GAS CON 2011; 5(6): 1559-1565.

[101]

U.S. Energy Information Administration, Annual Energy Outlook 2015; DOE/EIA0383(2015)

[102]

Willems GP, Golombok M, Tesselaar G, Brouwers JJH. Condensed rotational separation


of CO2 from natural gas. AlChE J 2010; 56(1): 150-159.

[103]

Xu N, Dong J, Wang Y, Shi J. High pressure vapor liquid equilibria at 293 K for
systems containing nitrogen, methane and carbon dioxide. Fluid Phase Equilib 1992; 81:
175 186.

[104]

Yeo. Z. Y., Chew. T. L., Zhu. P. W., Mohamed. A. R, Chai. S. P. (2012). Conventional
processes and membrane technology for carbon dioxide removal from natural gas: A
review. Journal of Natural Gas Chemistry Vol. 21 No. 3.

[105]

Yang, R. (1997). Gas Separation by Adsorption Processes, Imperial College Press, ISBN
9781860940477, Singapore

[106]

ZareNezhad B, Hosseinpour N. An extractive distillation technique for producing CO2


enriched injection gas in enhanced oil recovery (EOR) fields. Energy Convers Manage
2009; 50(6): 1491-1496.

101

APPENDIX - I

102

Base Case for Single Packing Simulation


Initial parameters taken for simulation of carbon dioxide capture on cooled packing for
pure CO2 vapor (In S.I Unit)
Sl no.
Parameters

Value for pure CO2

Radius of packing (R)

0.005 m

Diameter of the packed bed (dia)

0.4018 m

Density of packing material (dp)

2546 kg/m3

Specific heat of Packing material (Cp)

840

Density of CO2 (den)

1.46 kg/m3

Density of CO2 frost (rf)

1562 (kg/m3)

Concentration of CO2 (yco2)

Viscosity of flowing gas (v)

1.04*10-5 kg/(m. s)

Initial Void fraction of packed bed (e)

0.637

10

Diffusivity of the System (D)

0.163*10-4 m2/s

11

Thermal Conductivity of gas (K)

6.2*10-3 (W/m-K)

12

Thermal Conductivity of CO2 frost (kf)

0.7 (W/m-K)

13

Boltzmanns Constant (kb)

1.3806488*10-23

14

Energy Barrier (Ed)

0.5*10-19

15

Nucleation Constant (kso)

1*10-6

103

16

Interfacial Tension ()

0.004 N/m

17

Antoines constant (A)

9.81060

18

Antoines constant (B)

1347.790

19

Latent Heat of De-sublimation of CO2 (y)

572834.27

List of variables used for simulation of carbon dioxide capture on cooled packing for pure
CO2 vapor

Sl no.

Variables

Initial Conditions

Bulk Pressure (Pb)

3 atm

Ambient Temperature in the experiment (Ta)

203 K

Initial Time (t)

Initial Temperature of the subcooled packing (Tin)

155.3183 K

Initial Thickness of Frost Layer (delin)

10-8 m

104

APPENDIX - II

105

Base Case for Multiple Packing Simulation


Initial parameters taken for simulation of carbon dioxide capture on cooled packing for pure CO2
vapor (In S.I Unit)

Sl no.

Parameters

Value for pure CO2

Radius of packing (R)

0.005 m

Diameter of the packed bed (dia)

0.4018 m

Density of packing material (dp)

2546 kg/m3

Specific heat of Packing material (Cp)

840

Density of CO2 (den)

1.46 kg/m3

Density of CO2 frost (rf)

1562 (kg/m3)

Concentration of CO2 (yco2)

Viscosity of flowing gas (v)

1.04*10-5 kg/(m. s)

Initial Void fraction of packed bed (e)

0.637

10

Diffusivity of the System (D)

0.163*10-4 m2/s

11

Thermal Conductivity of gas (K)

6.2*10-3 (W/m-K)

12

Thermal Conductivity of CO2 frost (kf)

0.7 (W/m-K)

13

Boltzmanns Constant (kb)

1.3806488*10-23

14

Energy Barrier (Ed)

0.5*10-19

15

Nucleation Constant (kso)

1*10-6

16

Interfacial Tension ()

0.004 N/m

17

Latent Heat of De-sublimation of CO2 (y)

572834.27

106