Accepted Manuscript

Title: Performance enhancement using multiple cryogenic

desublimation based pipeline network during dehydration and
carbon capture from natural gas

Author: Abulhassan Ali Khuram Maqsood Ali Redza Karen

Hii Azmi B.M. Shariff Saibal Ganguly

PII: S0263-8762(16)00034-4
DOI: http://dx.doi.org/doi:10.1016/j.cherd.2016.01.020
Reference: CHERD 2159

To appear in:

Received date: 16-5-2015

Revised date: 29-11-2015
Accepted date: 19-1-2016

Please cite this article as: Ali, A., Maqsood, K., Redza, A., Hii, K., Shariff,
A.B.M., Ganguly, S.,Performance enhancement using multiple cryogenic
desublimation based pipeline network during dehydration and carbon capture
from natural gas, Chemical Engineering Research and Design (2016),
http://dx.doi.org/10.1016/j.cherd.2016.01.020

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 Highlights

1. Cryogenic multiple bed network was proposed for natural gas purification

2. Investigation of process parameters achieved at atmospheric pressure

3. Cryogenic liquid and solid formation was quantified at higher pressures

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4. Cryogenic Multiple Equilibrium Temperature modeling showed promise

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Page 1 of 38
Performance enhancement using multiple cryogenic desublimation based pipeline

network during dehydration and carbon capture from natural gas

Abulhassan Ali, Khuram Maqsood, Ali Redza, Karen Hii, Azmi B. M. Shariff,

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Saibal Ganguly*

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Chemical Engineering Department

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Universiti Teknologi PETRONAS

Bandar Sri Iskandar, 31750, Perak, Malaysia.

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Corresponding author: Prof. Dr. Saibal Ganguly, Chemical Engineering Department,

Universiti Teknologi PETRONAS, Bandar Sri Iskandar, 31750, Perak, Malaysia.

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Presently at:
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Chemical Engineering Department, BITS-PILANI, GOA Campus, India 403726

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Tel: +91 7219571392, +91 832 2580241; E-mail: gangulysaibal2011@gmail.com

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Page 2 of 38
 Abstract

Cryogenic carbon capture from natural gas at high pressures requires accurate process

synthesis and determination of process parameters due to the presence of solid-vapor and

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vapor-liquid-solid equilibria. At high pressures, the higher liquid formation not only

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causes operational problems, but also induces hydrocarbon losses in cryogenic packed

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beds. The present study proposes a novel multiple cryogenic desublimation based pipeline

network with its sections at different cryogenic pressures and temperature profiles to

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enhance the separation. The experimental study explores the simultaneous separation of

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water and carbon dioxide from ternary feed gas mixture (CH4-CO2-H2O) by using multiple

counter current cryogenic desublimation beds.

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A novel simulation strategy using multiple equilibrium temperature (MET) concept is also

introduced for simulation studies. Simulation studies were subsequently conducted for
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both atmospheric and high cryogenic bed pressures and compared with experimental

measurements. The effect of ambient humidity on dehydration was also investigated

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experimentally and it was observed that the humidity has significant effects on
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dehydration due to back diffusion. The effect of some important parameters like bed

length, feed gas pressures, bed temperatures, feed flow rates and feed gas pressures for
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separation were investigated. Experimental investigation was also conducted to quantify

liquid formation and vapor-solid equilibrium at high pressures. The experimental results of

desublimation based cryogenic pipeline network showed promising potential for industrial

exploitation.

Page 3 of 38
 Keywords: Cryogenic CO2 capture; Multiple Cryogenic beds; Natural gas; pipeline based

CO2 removal; Dehydration

1 Introduction

Natural gas has emerged as one of the cleanest, safest and most useful sources of energy

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in the world. It fulfils the global requirements for producing high quality, economic and

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sustainable clean energy [1]. Although natural gas is widely hailed as clean fuel compared to

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other fossil fuels, raw natural gas consists largely of methane along with impurities such as

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water, carbon dioxide, and other higher hydrocarbons.

Among the several processes used for the purification of natural gas, absorption is
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extensively used for dehydration and removal of CO2 and other impurities. However, it uses

chemicals and may cause emission of hazardous volatile organic compounds, which may
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restrict its future application in natural gas purification [2]. The cryogenic process is an

emerging alternative for carbon capture and purification of natural gas, which needs
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systematic research for future applications. The cryogenic separation processes can be
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classified into three categories namely; conventional, non-conventional and hybrid methods

and are already cited in literature by Maqsood et al. [3-5] and Ali et al. [6, 7].
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Desublimation based cryogenic separation of CO2 from natural gas is a physical

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separation. Desublimation is the reverse or the anti-sublimation process, which can be

defined as "the transition of a substance directly from the gas to the solid phase without

passing through the intermediate liquid phase. Maqsood et al. [3] has reviewed the

cryogenic desublimation processes available in the existing literature. The basic concept of

cryogenic desublimation based separation is based on the difference in the freezing points of

the components of natural gas. At atmospheric pressure, CO2 and CH4 have freezing points of

Page 4 of 38
-78.5 and -182.5 0C respectively, and it is convenient to separate the mixture of these

components on the basis of differences in freezing points. CO2 desublimate on the surface of

pre-chilled packing and CH4 passes without any phase change. The desublimation process

can occur both under atmospheric pressure or higher pressures. Subsequently, the

desublimated solid CO2 can be converted into vapor or liquid phase using already recovered

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carbon dioxide at atmospheric temperature.

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In 2002, Clodic and Younes [8-10] demonstrated anti-sublimation based CO2 capture

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process where CO2 frosts on the surface of heat exchangers. The authors reported that, the

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energy penalty for their process is lower compared to MEA absorption. A novel process for

CO2 capture from flue gases using cryogenic packed bed was developed by Tuinier et al [11-
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14]. Song et al. [15, 16] exploited cryogenic separating system using Stirling coolers for CO2

capture from flue gases. In 2012, an experimental setup was developed by Nor Syahera [17]
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for CO2 removal from a binary mixture of CH4 and CO2. In 2014, Ali et al. [6, 18] presented
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single cryogenic packed bed based simulation and experimental studies for minimization of

energy consumption during separation of binary CH4-CO2 mixtures.

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Most processes reported in the literature involve either CO2 capture from industrial flue
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gases, biogas or binary mixtures. Also separation at high pressures have hardly been studied

and most of the studies used one average temperature to represent the process. In available
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literature, the removal of water and CO2 from flue gases was studied using a single cryogenic

packed bed [11]. A single average temperature was taken for each bed. The resultant CO2

product may get mixed with H2O and the energy requirement is also higher. Furthermore, the

dehydration of natural gas using multiple cryogenic packed beds is not available in existing

Page 5 of 38
literature. The effect of process parameters due to the presence of additional natural gas

components, during desublimation based separation, is hardly reported in literature.

In the present work, multiple cryogenic desublimation bed pipeline network has been

synthesized in the pipeline sequence and presented for simultaneous dehydration and CO2

removal from natural gas. The objective of the present study is to propose and develop the

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framework of desublimation pipeline network and investigate the suitable operational

conditions like temperatures and pressures for desired separation. A high pressure pipeline

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under cryogenic temperature profile can be represented as a series of equilibrium flash

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separations. A novel simulation strategy, based on multiple equilibrium temperatures (MET)

was proposed for both high feed gas pressures as well as atmospheric pressure. The present
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study explores the concept of multiple cryogenic bed pipeline network along with the studies

on the effects of the different process parameters like environmental humidity, feed and bed
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pressures, flow rates, compositions and bed temperatures on separation.
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The schematic diagram of a multiple cryogenic desublimation based pipeline network

with three cryogenic beds is shown in Figure 1. The first bed is used for dehydration. If the
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associated water removal to the desired level is not achieved in the first bed, then the second
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bed is also employed for the dehydration purpose. The third bed is used for CO2 removal.

Additional beds may also be employed in the pipeline network if other hydrocarbons are
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present. Each bed is operated at its optimal conditions for the specified duty of separation.

Page 6 of 38
 t
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Figure 1: Schematic diagram of a sample cryogenic desublimation based pipeline network
consisting of three cryogenic packed beds.
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The present study shows a comparative study of the simulation results and the

experimental data for cryogenic desublimation based pipeline network. The multivariable
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optimization of the high pressure multiple bed multi-component cryogenic pipeline network

is presently being undertaken and will be reported in future studies.

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2 Process analysis for cryogenic separation under high pressures

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Cryogenic separation requires accurate thermodynamic analysis due to both liquid and

solid CO2 formation in the range of operation. The accurate prediction of CO2 is essential to
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avoid the operational problems in cryogenic beds. Moreover, the higher liquid formation also

may cause higher hydrocarbon losses. The analysis of solid-vapor (V-S) and solid-vapor-

liquid (V-L-S) phase needs to be studied to derive the separation characteristics. The triple

point of carbon dioxide occurs at a pressure of 5.2 bar and -56.4 0C. The desublimation

temperature of CO2 at 1 bar is -78.5 0C. At this pressure and temperature, the liquid phase is

Page 7 of 38
not stable. The gas simply converts into a solid and it does not go through a liquid state

during this phase transition [6]. Within a temperature range between -56.6 0C and 310C and

pressure greater than 5.2 bar and less than 74 bar respectively CO2 is in its liquid state except

at very high pressures. This means that, below 5.2 bar, CO2 exists only in its solid or gaseous

state. At 5.2 bar and - 56.4 0C, all the three states (solid, liquid and gas) are present.

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Pipeline pressure has significant effect on the solid-vapor region in the phase envelop. At

low pressures, the solid-vapor region is wide and favors easy separation at low temperature.

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Figure 2 depicts the effect of pressure on the phase envelop for binary mixtures of CO2 and

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CH4 [19]. The top curve in the Figure 2 represents the dew point while the bottom curve

represents the bubble point line. The area above the dew point line shows the vapor region
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and the area below the bubble point represents the liquid region. The shaded area in the phase

envelop represents the solid-vapor region. It is elucidated from Figure 2 that by increasing the
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pressure, the solid-vapor region narrows down. Furthermore, the solidification at lower
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pressures has wider temperature ranges, for example, in the Figure 2(a), the solidification

temperature ranges from -59 0C to -106 0C. Figure 2 also shows that at lower pressure, the
pt

higher percentage of saturated CO2 liquid is converted to solid and by increasing the pressure,

the percentage of saturated CO2 liquid conversion to solid decreases. For example, a saturated
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liquid of 92% CO2 at 20 bar convert to solid CO2, while 62% of CO2 at 40 bar convert to
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solid CO2. The vapor liquid (V-L) and liquid solid regions (L-S) are also marked on the T-x-y

diagram in Figure 2.

Page 8 of 38
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Figure 2: Effect of pressure on the phase envelop of methane and carbon dioxide up to 45 bar

Page 9 of 38
3 Experimental studies on multiple bed desublimation network with binary and

ternary gas mixtures at atmospheric and high pressures

In the present study, experimental setups were fabricated to validate the concept of

multiple bed desublimation network using ternary feed gas mixtures at atmospheric pressure

and binary feed gas mixtures at high pressures. Case study 1 deals with the ternary CH4-CO2-

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H2O mixture at atmospheric pressure while case study 2 comprises of binary CH4-CO2

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mixture at high pressures. Quantification of liquid and solid formed at high pressure has been

carried out under case study 2.

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3.1 Case study 1: Experimental study on multiple cryogenic desublimation pipeline
network at atmospheric pressure an
Multiple cryogenic desublimation beds were employed for studies on dehydration and
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CO2 removal. The physical detail of the bed are shown in Table 1. Figure 3 shows the

experimental setup for conducting the studies on multiple bed pipeline network. The packed
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beds were constructed with stainless steel and glass balls were used as packing material.

Several thermocouples were used to investigate the temperature changes during cooling and
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capture cycles. Humidity probes were installed to investigate the moisture contents. The
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temperature ranges used for the dehydration were 0 0C to -30 0C. The feed gas first entered in

the humidifier, where water content was increased in the feed. The purpose of the humidifier
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was to attain the wellhead moist feed gas conditions artificially. The quantity of water was

controlled either by spraying or by introducing the steam along with feed gas. The humid

feed entered the dehydration unit, where associated water was removed either in a single or

dual pipeline sections. After the removal of water, the feed gas entered in the CO2 removal

pipeline section. The average temperature of the CO2 removal bed for was kept at -93 0C.

Page 10 of 38
After CO2 capture, the samples were analyzed by using the gas chromatography unit

(SHIMADZU GC 2010) and online infra-red gas analyzer (MRU Vario Plus).

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Figure 3: Experimental setup representing cryogenic pipeline network for dehydration
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Table 1: Physical Properties of dehydration packed bed with varied bed length

Dehydration Dehydration CO2

bed 1 bed 2 removal bed
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conditions conditions conditions

Length of bed (m) 0.46 0.9 0.46
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Diameter of bed (m) 0.0418 0.0418 0.0418

Porosity 0.62 0.62 0.64

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Mass of packing (kg) 1.0 2.0 1.0

Density of packing (kg/m3) 2562

Diameter of packing (m) 0.01

If the required removal of water was not achieved in one pipeline bed, then a second

pipeline section was used for the dehydration purpose. The effects of back diffusion, bed

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Page 11 of 38
temperature and feed flow rate were also studied along with separation using the

desublimation based pipeline network.

3.1.1 The effect of environmental humidity through back diffusion on dehydration

The environmental humidity has a significant effect on the final water content of the gas

stream. This effect was examined with two different setups. In the first case, a desiccator was

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placed near the output of the pipeline sufficiently at a distance after the humidity probe

location for outlet gas from the dehydration section and adjusted in a way to minimize the

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effect of the environment humidity effect. The second case showed the dehydration setup

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without the desiccator, which permits the back diffusion from the product tank into the

pipeline. The desiccant only reduces the back diffusion effect from the environment to the
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experimental system. The effect of back diffusion is shown in Figure 4 . The effect of back

diffusion on percentage removal of water is provided in Table 2. It is elucidated from the

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results that by eliminating back diffusion, more dehydrated product gas can be achieved. The
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effect tapers off when residence time in the bed is high.

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Page 12 of 38
 16
Without back diffusion (65% ambient environmental humidity)

14 Without back diffusion (90% ambient environmental humidity)

Extrapolated curve

12 With back diffusion

Relative Humidity (g/m3)

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4

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2

0
0 20 40 60 80 100 120 140 160
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Time (s)

Figure 4: Experimental measurement for dehydration with and without back diffusion
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Table 2: Effect of back diffusion on percentage removal of water as measured at the outlet
of dehydration bed in the cryogenic pipeline network
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Percentage
Output water contents
removal of water
Bed Initial water
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temperature contents With Without

With back Without back
back back
diffusion diffusion
diffusion diffusion
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0
C (kg/kg dry gas) (kg/kg dry gas) (kg/kg dry gas) % %
0 0.0122 0.0030 0.0015 75.4 87.7
-10 0.0122 0.0020 0.001 83.6 91.8
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-20 0.0122 0.0013 0.00065 89.3 94.6

-30 0.0122 0.00075 0.000378 93.8 96.9

3.1.2 Effect of feed flow rate on dehydration

The effect of feed flow rate on dehydration was investigated using initial bed temperature

of -200C. The effect of flow rate on dehydration can be observed from Figure 5. It is evident

from Figure 5 that for higher flow rates, more water was captured within the bed than for

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Page 13 of 38
lower flow rate like 2 liters/min. Also for a shorter residence time, higher flow rates provide

sharper changes in water removal. It was also observed during experimentation that flows

above 30 to 40 liters/min do not show an increase in water removal.

0.012
2 Lpm
5 Lpm

t
0.01 20 Lpm

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Moisture content (kg / kg dry gas)

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0.008

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0.006

0.004

0.002
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0
0 5 10 15 20 25 30 35
Time (S)
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Figure 5: Effect of feed flow rate on cumulative water removal

3.1.3 Effect of bed temperatures

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The initial bed temperature has a significant effect on dehydration and experimentations
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were conducted with different initial bed temperatures. The comparative effect of five

different initial bed temperatures on dehydration is shown in Figure 6. The experimentation

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was conducted on temperature from 0 0C to -30 0C. At 0 0C, the moisture content per kg dry

gas was recorded to be 0.003 kg after 35 seconds. At -30 0C, after the same time interval, the

moisture content dropped down to 0.00075 kg per kg dry gas, indicating substantial removal

of water with the decrease in bed temperature. The effect was observed to slow down

considerably after -30 0C.

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Page 14 of 38
 0.014
0 -5 -10

0.012 -20 -30

Moisture content (kg/kg dry gas)

0.01

0.008

t
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0.006

0.004

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(75.4 %)
0.002 (83.6 %)

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(89.3 %)
(93.8 %)
0
0 5 10 15 20 25 30 35 40
an Time(s)

Figure 6: Effect of initial bed temperature on reduction of moisture content at the exit of
dehydration bed. Percentage removal is shown in parenthesis
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3.1.4 Effect of bed length on dehydration

The increase in length of the bed provides more residence time for wet gas. The effect of
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bed length on dehydration is shown in Figure 7. It is evident that with the increase in length,
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the outlet humidity of the gas decreased. But a further increase in the bed length had no

significant effect on the dehydration. With a bed length of 0.3 m, the outlet concentration was
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found to be 3.6 g/m3 whereas by increasing length to 0.9 m the concentration was decreased

to 1.9 g/m3. A further increase in the length, for example, 1.22 m results in exit concentration
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of 1.5 g/m3. These results show that by increasing the bed length, the amount of water

captured also increases significantly, but further increase in the length does not have a

significant effect.

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Page 15 of 38
 16
Bed length 0.3 m
14 Bed length 0.9 m
Bed length 1.22 m
12
Concentration (g/m3)

10

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6

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2

0
0 20 40 60 80 100 120 140 160
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Time (s)

Figure 7: Effect of bed length on dehydration

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3.2 Case study 2: Experimental study on quantitative analysis of liquid formation and
vapor-solid equilibrium at high pressures
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During desublimation at high pressures, all three phases namely vapor-liquid-solid (V-L-

S) exist together. The operation of high pressure packed beds needs specialized operating
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procedures to be evolved through systematic research. Also the presence of a liquid phase at
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different operating conditions may lead to operational problems. This effect needs to be

separately understood and resolved.

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The experimental setup illustrated in Figure 8, as reported by Maqsood [20], was used in

the present work to investigate the composition and temperature-pressure boundaries for

cryogenic liquid formation. The main component of the experimental setup consists of a flash

vessel with outer jacket, gas feeding system and refrigerant supply system. The flash vessel

consists of mainly two parts, the top portion is for feed gas supply and vapor phase

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Page 16 of 38
measurements and bottom section is used for liquid accumulation and liquid phase

measurements. The inner diameter of the upper part is 3 inches with 16 inch length while the

bottom part is designed for liquid collection with 1 inch diameter with 12 inch length. For

uniform temperature distribution in the jacket during the cooling cycle, multiple inlets were

used for the introduction of the liquid nitrogen as refrigerant or coolant. Several

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thermocouples were used to investigate the temperature variation in both the vessel and the

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outer jacket. The liquid level measurement transmitter was installed at the bottom of the

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vessel. The gas feeding system along with the compressor was used to achieve the desired

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pressure. Two heaters were installed on top and bottom of the vessel outlet to increase the

temperature of the product streams to 5 0C due to the operational limits of the composition
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measurement using IR analyzer. Two sampling devices were attached to the system for top

and bottom product, which were further transferred to the sampling bags for gas
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chromatography analysis (SHIMADZU GC 2010). The infrared analyzer provided real-time

online measurements while GC analysis provided periodic calibration of IR instrumentation.

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The temperature and pressure of the vessel were measured and kept constant during the

experimentation in order to get the equilibrium points. All real-time data were collected
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using a computer based data acquisition and recording system. The schematic of the
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experimental setup is shown from Figure 9.

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Page 17 of 38
 t
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Figure 8: Experimental setup for quantification of liquid and solid formation at high
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pressures
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Figure 9: Schematic diagram for experimental setup used for quantification of liquid and

solid formation during cryogenic separation

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Page 18 of 38
3.2.1 Experimental measurements at high pressures for quantitative analysis of liquid
and solid formation

The experimental results for V-L-S and V-S phases are discussed in this section. In the

experimental setup detailed in Figure 8 and Figure 9, the feed gas splits into two or three

phases and the liquid formation is observed so that the liquid level is quantified with suitable

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instruments. The second set of data is obtained in the temperature and pressure range where

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the feed splits into primarily solid and vapor phases. The steady state experimentation was

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carried out at different feed compositions and vessel operating conditions. Since advanced

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control was not applied to the equipment, the pressure may have a load disturbance up to 2

bar during the operation. The temperature distribution and composition in the separator were

continuously recorded and are presented in Table 3. an

Table 3: CO2 liquid formation at higher pressures
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P T Composition Liquid
(bar) 0
( C) Liquid Vapor Formation
(kg)
CO2 CH4 CO2 CH4
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-23 0.810 0.190 0.460 0.540 0.000

-27 0.850 0.150 0.340 0.660 0.000
20 -48 0.948 0.052 0.318 0.682 0.048
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-60 0.915 0.084 0.210 0.790 0.053

-70 0.896 0.103 0.105 0.895 0.009
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-22 0.830 0.170 0.288 0.712 0.058

-32 0.962 0.038 0.195 0.805 0.110
40 -41 0.981 0.019 0.141 0.859 0.134
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-52 0.991 0.009 0.069 0.931 0.140

-63 0.829 0.171 0.288 0.712 0.000

It is elucidated from Table 3 that the decrease in the bed temperature leads to higher

liquid formation. Once the temperature reaches the desublimation point of CO2, the liquid

disappears and the operation enters into the vapor-solid region. Subsequently, the solid

formation during separation was calculated by conducting experimentation in the vapor-solid

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Page 19 of 38
region of the phase equilibria. The experimentation was conducted at different pressures

varies from 20 to 40 bar. The experimental results are shown form Table 4 and Table 5.

Further decrease in the temperature leads to the liquid-solid region of the phase equilibria.

For example, at 20 bar, maximum solid formation was achieved at -90 0C, which is the

working boundary for this pressure. Further lowering of the temperature leads to the L-S

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region.

Table 4: Experimental quantification of CO2 solid formation at different temperatures at 20

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bar pressure

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20 bar
Inlet Outlet
Temperature
Component Mole Mass
Mole Mass 0
( C) fraction Vapor Solid

CH4
fraction

0.3
(kg)
0.0425
an 0.8243
(kg) (kg)
0.0425 0.0000
-70
CO2 0.7 0.2720 0.1757 0.0249 0.2471
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CH4 0.3 0.0425 0.8879 0.0425 0.0000
-80
CO2 0.7 0.2720 0.1121 0.0147 0.2573
CH4 0.3 0.0425 0.9250 0.0425 0.0000
-90
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CO2 0.7 0.2720 0.0750 0.0095 0.2625

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Table 5: Experimental quantification of CO2 solid formation at different temperatures at

40 bar pressure
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40 bar
Inlet Outlet
Temperature
Component Mole Mass
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Mole Mass 0
( C) fraction Vapor Solid
fraction
(kg) (kg) (kg)
CH4 0.3 0.0944 0.8164 0.0944 0.0000
-63
CO2 0.7 0.6044 0.1836 0.0582 0.5462
CH4 0.3 0.0944 0.8278 0.0944 0.0000
-65
CO2 0.7 0.6044 0.1722 0.0539 0.5505
CH4 0.3 0.0944 0.8771 0.0944 0.0000
-70
CO2 0.7 0.6044 0.1229 0.0363 0.5681

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Page 20 of 38
4 Simulation results using multiple equilibrium temperature (MET) representation of
the cryogenic packed bed

The present work attempts to represent the high pressure regions of the cryogenic packed

bed operation using a new concept of model development. The packed bed is represented as a

series of equilibrium flash stages with the assumption that the liquid formed at each

t
equilibrium stage is immediately removed from the system. The model formation may be

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used as a gross overall lumped single equilibrium temperature (SET) model or a distributed

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multiple equilibrium temperature model (MET). The MET representation is essentially a

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sequence of SET segments in the pipeline. The benefit of modeling using the proposed

structure of lumping is that the models have the flexibility to be located at the physical
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cryogenic measurement points and three phase systems can be modeled and validated

conventionally. This lumped model may be used for online predictive applications also in
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future research on online optimization and control of cryogenic packed beds under pressure.
ed

In the MET representation, each point in the cryogenic packed bed was considered as a

flash equilibrium stage. The whole bed can be assumed as a series of flash equilibrium stages.
pt

Feed enters in the flesh stage 1, which is at uniform temperature, and is split into three

phases. Now the top product (vapor phase) enters into the second flash stage and converts
ce

into solid phase or frost on the surface of the packing. The feed which converts into liquid
Ac

accumulates at the bottom of the bed and is removed. The general schematic for this concept

of modeling is presented in Figure 10. The assumptions used in this model are (1) The feed

composition in each stage is uniform and the packing in the bed ensures good mixing (2) The

temperature at each point within the flash stage is uniform (3) The liquid formed does not

participate in any future stages and the milky liquids are considered as liquid phase only.

21

Page 21 of 38
 The equilibrium predictions were obtained by using an Aspen Hysys simulator along with

modified Peng-Robinson EoS.

t
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Figure 10 : Multiple equilibrium temperature (MET) representation of cryogenic packed
bed
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It is illustrated in Figure 10 that six thermocouples are installed in each single packed bed

section, and the location of each thermocouple represents a SET segment. After the cooling
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cycle, the bed reached a temperature profile where the temperature at the feed inlet point

(z=0) is higher as compared to the outlet (z=1). Once the desired temperature of the bed is
pt

reached, the feed gas supply is started, so at t > 0 the feed gas entered the first flash section
ce

where it splits into either V-S or V-L-S phases. This phase split depends on the flash section

temperature, feed composition and bed pressure. The solid phase frost on the surface of the
Ac

packing while the liquid phase is assumed to be removed from the bottom of the bed. The

vapor phase from flash section 1 further enters into the flash section 2 where it splits again.

The resultant composition of methane in vapor phase after each flash section increases. If the

temperature of any flash section is below the desublimation point (where desublimation point

strongly depend upon the pressure and composition), then the CO2 frosts on the surface of the

packing. The full range of experimentation was conducted for binary mixtures of gases.

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Page 22 of 38
 An important preliminary simulation study was conducted to investigate the effect of

higher hydrocarbon on the CO2 concentration in the product. The simulation results using

MET model are shown in Figure 11. It was observed that the higher hydrocarbon separated in

the SET1 and the exit vapor phase from SET1 is enriched CH4. The feed enters in the SET1 at

25 0C and the temperature of the SET1 is maintained at -75 0C. At this temperature and

t
pressure, the stream splits into solid, liquid and vapor phases. The vapor phase further enters

ip
into the SET2 which is maintained at -81 0C. Although there is a small fraction of ethane and

cr
propane also present in the stream, but the phase behavior shows that this small fraction does

us
not have any significant effect on separation characteristics. The phase envelop of binary

mixture of methane and CO2 is still valid for this stream. The exit vapor stream of the SET1
an
enters into the SET2 where the stream splits into solid and vapor phase only. It can be

observed from Figure 11 that the thermodynamic behavior of these components was similar
M
to the binary mixture of CO2 and CH4 and the deviation is quite narrow.
ed
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23

Page 23 of 38
 80
Natural gas
70 Binary

60
CO2 Concentration (%)

50

40

t
ip
30

cr
20

10

us
0
0 0.2 0.4 0.6 0.8 1 1.2
an
Axial Position (z)

Figure 11: Comparison of exit vapor phase composition for binary CH4-CO2 mixture and
M
natural gas
ed

4.1 Simulation results for MET model for natural gas

Simulation study was conducted initially using a feed comprising of the binary
pt

component with 70 mole% CO2 and 30 mole% CH4 at pressure 20 bar and with the

temperature profile of [-75, -81,-87,-93,-98,-104] 0C. Six flash stages are considered for this
ce

simulation study based on the thermocouple locations, for example the SET1 is at -75 0C and

SET6 is at -104 0C. The first iteration at t > 0 is the starting point of the capture cycle and the
Ac

feed gas is introduced at 25 0C. The simulator shows the solid formation at these conditions,

which can be further verified from phase diagram. At these conditions, the feed splits into

solid and vapor phase only, so that the liquid formation at these conditions can be avoided.

The mole fraction of the CO2 in the vapor phase is 0.089 whereas the mole fraction of CH4 is

0.911. These results show that the product gas contains higher amount of CH4.

24

Page 24 of 38
 Now this product gas becomes the feed for the SET2 where the operating temperature is

810C. It is assumed that the product gas will leave the SET1 at same temperature i.e. 750C.

The operating conditions of SET2 will allow the feed gas to split into solid-vapor phases only.

The CO2 frosts on the surface of the packing and enriched methane product enters into the

SET3. Similarly, the feed gas passes through the remaining flash segments and the exit

t
product gas from SET6 has a composition of 0.983 CH4 (mole fraction). The results of

ip
simulation using MET model are presented in Figure 12. The coupled variations of

cr
concentration and temperature with time and space dimensions show that the CO2

us
concentration in vapor phase increase with increase in time and axial position. For example,

the CO2 concentration after 16 seconds at outlet of MET6 (z=1), is 0.017 mole fraction and
an
after 288 seconds it is 0.1 mole fraction. Once the bed is near saturation point, the change in

concentration is very rapid and in 10 seconds it reaches at 0.7 mole percent. This shows that
M
the bed is not able to capture CO2 anymore. The recovery cycle should start at an appropriate

time.
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25

Page 25 of 38
 t
ip
cr
us
an
M
ed
pt
ce
Ac

Figure 12: Responses of temperature and concentration in time and space dimensions

within the cryogenic packed bed using MET simulation model

26

Page 26 of 38
4.2 Comparison of MET simulation and experimental results

The MET model results were compared using CO2 concentration in the product stream at

z=1 with the experimental data and are presented in Figure 13. As mentioned earlier, the

concentration was experimentally measured only at the outlet (z=1) of the bed. The

experimental measurements of the concentration variations within the bed were not found

t
practically realizable. Figure 13 shows that the model prediction has a good resemblance with

ip
simulation results with mean absolute percentage error 16.6 %. The reason for comparatively

cr
higher deviation is that the milky liquids formed during cryogenic experimentation at higher

us
pressures are considered as clear liquid during material balance in simulation studies.

100
MET model

Experimental measurements
an
80
M
CO2 Concentration at z=1 (%)

60
ed

40
pt
ce

20
Ac

0
0 50 100 150 200 250 300 350
Time (s)

Figure 13: Comparison of CO2 concentration at pipeline exit (z=1) using MET model and
experimental measurements

27

Page 27 of 38
4.3 Investigation of operation boundaries and quantification of liquid and solid
formation during cryogenic separation

The effects of bed pressure and temperature on CO2 removal and phase separation is

simulated in this section. The feed gas pressure was selected to be 20 to 40 bar with the

temperature range -10 to -110 0C. Table 6 presents the results for 20 and 40 bar pressure. In

t
the first case, feed entered the bed, which is maintained at 20 bar and -30 0C. At this

ip
temperature and pressure the feed gas is passed through the bed without any phase change. A

cr
further decrease in the bed temperature causes the feed to split into vapor-liquid phases. The

us
bed temperature range for this split, varies from -40 0C to -60 0C. The solid formation starts

from -70 0C where the feed splits into solid-vapor phases. The solid phase only contains CO2,
an
whereas the vapor phase contains both CO2 and CH4. It is also elucidated from Table 6 that

the decrease in temperature results in the increase in product purity. For example, at -70 0C
M
the percentage of methane in the product is 68.75%. On the other hand, at -100 0C, the

percentage is 98.2%. These results show that low temperature operation favors the higher
ed

product purity.
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Page 28 of 38
 t
ip
cr
Table 6: Effect of bed temperature on separation by simulation at 20 and 40 bar pressure

Feed Conditions Mass in (kg) Mass out (kg)

us
Phase
P (bar) T (0C) Vapor Liquid Solid Total mass out
split
CO2 CH4 Total CO2 CH4 Total CO2 CH4 Total CO2 CO2 CH4
-30 0.067 0.011 0.078 0.067 0.011 0.078 0 0 0 0 0.067 0.011 V

an
-40 0.067 0.011 0.078 0.032 0.010 0.041 0.036 0.001 0.036 0 0.067 0.011 V-L
-50 0.067 0.011 0.078 0.015 0.009 0.025 0.052 0.001 0.053 0 0.067 0.011 V-L
-60 0.067 0.011 0.078 0.008 0.009 0.017 0.059 0.002 0.061 0 0.067 0.011 V-S

M
20
-70 0.067 0.011 0.078 0.005 0.011 0.016 0 0 0 0.063 0.067 0.011 V-S
-80 0.067 0.011 0.078 0.002 0.011 0.013 0 0 0 0.065 0.067 0.011 V-S
-90 0.067 0.011 0.078 0.001 0.011 0.012 0 0 0 0.066 0.067 0.011 V-S

d
-98 0.067 0.011 0.078 0.0002 0.011 0.0112 0 0 0 0.067 0.067 0.011 V-S
-110 0.067 0.011 0.078 0 0 0 0 0.011 0.011 0.067 0.067 0.011 L-S

CO2 te
CH4 Total CO2 CH4 Total CO2 CH4 Total CO2 CO2 CH4
ep
-10 0.151 0.024 0.174 0.151 0.024 0.174 0 0 0 0 0.151 0.024 V
-20 0.151 0.024 0.174 0.075 0.021 0.095 0.076 0.003 0.079 0 0.151 0.024 V-L
-30 0.151 0.024 0.174 0.037 0.018 0.055 0.114 0.006 0.120 0 0.151 0.024 V-L
V-L
c

-40 0.151 0.024 0.174 0.019 0.015 0.033 0.132 0.009 0.141 0 0.151 0.024
40 -50 0.151 0.024 0.174 0.009 0.011 0.020 0.142 0.013 0.155 0 0.151 0.024 V-L
Ac

-60 0.151 0.024 0.174 0.003 0.006 0.009 0.148 0.018 0.166 0 0.151 0.024 V-L
-62 0.151 0.024 0.174 0.013 0.024 0.036 0 0 0 0.138 0.151 0.024 V-S
-64 0.151 0.024 0.174 0.009 0.024 0.033 0 0 0 0.141 0.151 0.024 V-S
-70 0.151 0.024 0.174 0.005 0.024 0.029 0 0 0 0.146 0.151 0.024 V-S
-80 0.151 0.024 0.174 0 0 0 0 0.024 0.024 0.151 0.151 0.024 L-S

Page 29 of 38
4.4 Comparison of simulation and experimental results for liquid and solid formation

Quantitatively, higher liquid formation was observed at high pressures. The comparative

studies between the simulation and experimental results for liquid and solid formations are

provided in Figure 14 and Figure 15. It can be observed that the solid region temperature for

20 bar starts from -60 0C when the liquid phase was transformed into solid, resulting in a

t
ip
steep change.

cr
0.25
Simulation results at 40 bar

us
Experimental measurements at 40 bar
Simulation results at 20 bar
0.2 Experimental measurements at 20 bar

an
Liquid formation (kg)

0.15
M
0.1
ed

0.05
pt

0
-80 -70 -60 -50 -40 -30 -20 -10 0
ce

Temperature (0C)

Figure 14: Quantitative comparison of cryogenic liquid formation at 20 and 40 bar using
simulation and experimental results
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Page 30 of 38
 0.70
20 bar, simulation
40 bar, simulation
0.60
20 bar, experimental
40 bar, experimental
0.50
Solid formation (kg)

0.40

t
ip
0.30

0.20

cr
0.10

us
V-S region V-L region

0.00
-100 -90 -80 -70 -60 -50 -40 -30 -20
an
Temperature (0C)

Figure 15: Quantitative comparison of cryogenic solid formation at 20 and 40 bar using
simulation and experimental results
M
5 Comparison of simulation and experimental results for cryogenic dehydration at
atmospheric pressure
ed

The simulation results for dehydration at atmospheric pressure using SET model are

presented in Table 7. The temperature of the bed varies from -5 0C to -30 0C at atmospheric
pt

pressure. It is elucidated from Table 7, the lower bed temperature results higher percentage
ce

separation. The experimental measurements and simulation results for dehydration at

different bed temperatures are compared in Figure 16. It is evident from Figure 16 that the
Ac

back diffusion has significant effect on dehydration and the resultant water content or

humidity deviates from the simulation results substantially. The mean absolute percentage

deviation with back diffusion is 6.7% while without back diffusion is 1.4 %. The simulation

results match satisfactorily with experimental results without back diffusion.

31

Page 31 of 38
 t
ip
cr
Table 7: Simulation results using SET model for different bed temperatures at atmospheric pressure

Feed Composition Bed conditions Composition(kg/h)

us
Water removed
P (bar) T (0C) Mole/h kg/h P (bar) T (0C) V L S (kg/h)
CH4 440.0 7058.9 7058.9 0.0

an
C2H6 50.0 1503.5 1503.5 0.0

C3H8 27.0 1190.6 1190.6 0.0

650.16

M
i-C4H10 10.0 581.2 581.2 0.0

n-C4H10 10.0 581.2 581.2 0.0

d
i-C5H12 10.0 721.5 721.5 0.0

80 25
te
n- C5H12

C6H14
1.0

1.0
72.2

86.2
1 -5 72.2

86.2
0.0

0.0
% Removal
ep
C7H16 0.5 50.1 50.1 0.0

C8H18 0.5 57.1 57.1 0.0

c

90.22
H2O 40.0 720.6 70.4 0.0 650.2
Ac

CO2 400.0 17603 17602 0.8

N2 10.0 280.1 280.1 0.0

1000.0 30507.1 29856.2 0.8 650.2

Page 32 of 38
 t
ip
cr
Feed Composition Bed conditions Composition(kg/h)
Water removed
(kg/h)

us
P (bar) T (0C) Mole/h kg/h P (bar) T (0C) V L S

CH4 440.0 7058.9 7058.9 0.0

an
C2H6 50.0 1503.5 1503.5 0.0

C3H8 27.0 1190.6 1190.6 0.0

672.98

M
i-C4H10 10.0 581.2 581.2 0.0

n-C4H10 10.0 581.2 581.2 0.0

i-C5H12 10.0 721.5 721.5 0.0

d
80 25 n- C5H12 1.0 72.2 1 -10 72.2 0.0 % Removal

te
C6H14 1.0 86.2 86.2 0.0
ep
C7H16 0.5 50.1 50.1 0.0

C8H18 0.5 57.1 57.1 0.0

93.39
c

H2O 40.0 720.6 47.6 0.0 673.0

Ac

CO2 400.0 17603 17602 1.0

N2 10.0 280.1 280.1 0.0

1000 29833.2 1.0 673.0

33

Page 33 of 38
 t
ip
cr
Feed Composition Bed conditions Composition(kg/h)

Water removed
P (bar) T (0C) Mole/h kg/h P (bar) T (0C) V L S

us
(kg/h)

CH4 440.0 7058.9 7058.8 0.0

an
C2H6 50.0 1503.5 1503.4 0.1

C3H8 27.0 1190.6 1190.2 0.4

712.29

M
i-C4H10 10.0 581.2 580.5 0.7

n-C4H10 10.0 581.2 580.0 1.2

i-C5H12 10.0 721.5 716.3 5.3

d
80 25 n- C5H12 1.0 72.2 1 -30 71.3 0.8 % Removal

te
C6H14 1.0 86.2 81.4 4.8
ep
C7H16 0.5 50.1 38.8 11.3

C8H18 0.5 57.1 23.3 33.8

98.85
c

H2O 40.0 720.6 8.3 0.0 712.3

Ac

CO2 400.0 17603 17601 2.8

N2 10.0 280.1 280.1 0.0

1000 29733.5 61.3 712.3

34

Page 34 of 38
 105
Simulation results
Experimental measuerments
100 with back diffusion
Experimental measurments
without back diffusion
95
Percentage Separation

90

t
ip
85

cr
80

us
75

70
-35 -30 -25 -20 -15 an
-10
Temperature (0C)
-5 0 5 10

Figure 16: Comparison of percentage separation using simulation results and experimental
M
measurements during dehydration at atmospheric pressure
ed

Conclusions

The present study attempts to synthesize and develop cryogenic removal of water and CO2
pt

from natural using multiple cryogenic desublimation based pipeline network. The advantages
ce

consist of clean, efficient pipeline based separation without chemicals or additives and with

low foot print or capital cost. Process parameters like bed temperature, feed flow rate, bed
Ac

length and the effect of environmental humidity during dehydration were investigated. The

cryogenic bed temperature has a significant effect on dehydration, where the percentage

removal of water increased from 75.4 to 93.8 % for bed temperatures from 0 0C to -30 0C.

The bed length affected dehydration up to a limit. Environmental humidity or back diffusion

showed a considerable effect on the dehydration process output. Elimination of back

diffusion enhanced separation from 87.7 to 96.6 % in the temperature range of 0 0C to -30 0C.

35

Page 35 of 38
Subsequent investigations were conducted on the quantification of liquid and solid formation

under cryogenic condition and high pressure. The decrease in the temperature resulted in

higher liquid and solid formation. From 20 bar to 40 bar pressure, liquid formation increased

and a steep change was observed in the range of -65 0C to -55 0C due to solid formation.

To summarize, dehydration and carbon capture was attempted experimentally through the

t
ip
synthesized cryogenic multiple bed desublimation based pipeline network both at

cr
atmospheric pressure and higher pressures under difficult measuring conditions.

Experimental quantification of liquid and solid formation under high pressure and cryogenic

us
conditions was achieved. A novel simulation strategy based on multiple equilibrium

temperature model (MET) was proposed and compared with experimental results. Natural gas
an
compositions were used for the simulation studies. The comparison of outlet concentration
M
measured experimentally showed a promising match with the simulation results.

Acknowledgment
ed

The authors would like to gratefully acknowledge the financial and infrastructural help

from Department of Chemical Engineering, Universiti Teknologi PETRONAS.

pt

References
ce

[1] J. G. Speight, Natural gas a basic handbook. Houston, Tex.: Gulf Pub. Co., 2007.
[2] A. J. Kidnay and W. R. Parrish, Fundamentals of Natural Gas Processing: CRC
Ac

Press, 2006.
[3] K. Maqsood, A. Mullick, A. Ali, K. Kargupta, and S. Ganguly, "Cryogenic carbon
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[4] K. Maqsood, A. Ali, A. B. M. Shariff, and S. Ganguly, "Synthesis of Conventional
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ip
[9] D. Clodic, R. El Hitti, M. Younes, A. Bill, and F. Casier, "CO2 capture by anti-
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cr
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M. Tuinier, M. van Sint Annaland, and J. Kuipers, "A novel process for cryogenic
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[14] M. J. Tuinier and M. van Sint Annaland, "Biogas purification using cryogenic
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pt

[15] C. F. Song, Y. Kitamura, and S. H. Li, "Evaluation of Stirling cooler system for
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ce

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bed," BTech project report, Universiti Teknologi PETRONAS, 2012.

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Graphical Abstract (for review)

i
cr
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Page 38 of 38