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BISWAJIT DEBNATH
Class Roll no: 001310302012
Examination Roll No: M4CHE1508
Registration No: 124707 of 2013-14
Session: 2013-2015
Signed: ___________________
Date: ___________
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:
________________________
Prof. (Dr.) Kajari Kargupta
Thesis Supervisor
Department of Chemical Engineering
Jadavpur University
Dean
Faculty of Engineering and Technology
Jadavpur University
CONTENTS
List of Figures
List of Tables
viii
Nomenclature
ix
Acknowledgement
ABSTRACT
CHAPTER 1: INTRODUCTION
4-23
24-39
40 52
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
Fig. 2
Fig.3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11
Fig. 12
Schematic diagram of a packed bed and a single packing with frost layer
Fig. 13
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
Fig. 18
Fig. 19
Effect of inlet gas flow rate on rate of deposition of frost layer thickness
Fig. 20
Fig. 21
Fig. 22
Effect of variation of carbon dioxide in feed gas stream on frost layer thickness
Fig. 23
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
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
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
vii
List of tables
Table no.
Description
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
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
CO2
ix
Cg
Tg
Ap
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 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.
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.
CHAPTER
1
INTRODUCTION
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%
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.
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.
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.
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
Hydrocarbons (C3+)
CO2
< 2 mol%
H2S
< 4 ppm
H2O
< 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.
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.
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.
1.2.2 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
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
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).
22
23
24
CHAPTER
2
LITERATURE REVIEW
25
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.
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
(bar)
-106 to 29
20-74
(1954)
Kaminishi et al.
- 50 to 10
24-200
CO2/CO/H2
(1968)
1968
TPxy
CO2-CH4
440-690
1971
PVTX
CO2-CH4, CO2-N2
-20 to 15
50-150
1971
PVTX
CO2-CH4-N2
-40 to 0
60-100
1976
TPxy
CO2-CH4
-43 to -23
9-85
1976
TPxy
CO2-CH4
-120 to -54
20-65
1978
TPxy
CO2-CH4
5-63
1978
TPxy
CO2-CH4, CO2-N2
-3
30-120
1983
TPxy
-54 to -23
5.8-160.15
(1978)
Al-Sahhaf et al.
N2
(1983)
Magee and Ely (1988)
1988
TPxy
CO2-CH4
-48 to 127
20-350
1989
TPxy
CO2-CH4, CO2-N2
-23 to 57
23-320
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
15 and 20
51.1-91.1
50-250
199-999
(1987)
N2
Seitz et al. (1996)
2002
PVTX
CO2-CH4-N2
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.
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.
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
38
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
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
44
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.
45
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
(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
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:
(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)
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.
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
= 26.876
= 25.957
= 25.311
= 26.335
= 51.60
.. 0.1% CO2
+ 4.08
(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)
(12)
(13)
49
50
3.5.1
Modeling
of
Desublimation
of
Carbon
dioxide
inside
the
( 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.
53
CHAPTER
4
RESULTS & DISCUSSION
54
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.
55
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
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
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
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
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
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
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
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
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
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
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
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
(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
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
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
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
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.
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
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
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
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
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
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.
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
88
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101
APPENDIX - I
102
0.005 m
0.4018 m
2546 kg/m3
840
1.46 kg/m3
1562 (kg/m3)
1.04*10-5 kg/(m. s)
0.637
10
0.163*10-4 m2/s
11
6.2*10-3 (W/m-K)
12
0.7 (W/m-K)
13
1.3806488*10-23
14
0.5*10-19
15
1*10-6
103
16
Interfacial Tension ()
0.004 N/m
17
9.81060
18
1347.790
19
572834.27
List of variables used for simulation of carbon dioxide capture on cooled packing for pure
CO2 vapor
Sl no.
Variables
Initial Conditions
3 atm
203 K
155.3183 K
10-8 m
104
APPENDIX - II
105
Sl no.
Parameters
0.005 m
0.4018 m
2546 kg/m3
840
1.46 kg/m3
1562 (kg/m3)
1.04*10-5 kg/(m. s)
0.637
10
0.163*10-4 m2/s
11
6.2*10-3 (W/m-K)
12
0.7 (W/m-K)
13
1.3806488*10-23
14
0.5*10-19
15
1*10-6
16
Interfacial Tension ()
0.004 N/m
17
572834.27
106