CHE 184-1P Process Control and Dynamics

Temperature Swing Adsorption Process Control for CO2 in Air Capture Using Zeolite as adsorbent

OVERVIEW

1. Brief description of the process

2. Identification and description of process variables and disturbances

3. Process dynamics/models

4. Block diagram

5. Control strategy description

6. Instrumentation

7. Piping and Instrumentation Diagram

8. References

Brief description of the process

A. Temperature Swing Adsorption

Temperature swing adsorption (TSA), also called as thermal swing adsorption, is a process cycle by which

adsorption is being taken place at low temperatures while further heating to significantly above the adsorption

temperature will drive the desorption process. Desorption is being done for the regeneration of the adsorbent used
[1]
in the process . TSA is commonly used for systems that has low concentration of adsorbate. Such of these

involve drying, sweetening, CO2 removal and pollution control. TSA process typically involves three steps. First

is the adsorption or production step at low temperatures, bed heating for desorption and cooling for regeneration
[2]
of adsorbents and bringing them back to the adsorption conditions . Initially, feed fluid which contains the

adsorbate is being passed through the adsorbent at certain temperature T1 and adsorbate partial pressure p1. This

will achieve an equilibrium loading n1. Heating step is being incorporated so as to increase the partial pressure of

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Temperature Swing Adsorption Process Control for CO2 in Air Capture Using Zeolite as adsorbent

the adsorbate at p2 and temperature T2, while maintaining the equilibrium loading n1. Any fluid that has an

adsorbate at less than p2 will tend to undergo desorption. Through purging, adsorbate are being recovered.

Subsequently, desorption will continue isothermally at temperature T2, which will further reach a certain pressure,

for example to p1 and at the same time a new loading n2. Cooling at maintained equilibrium loading n2, will bring

back the temperature T2 to adsorption temperature T1. At this point, the best-quality product from adsorbent will

be produced and therefore, the adsorbent will be ready again for the adsorption process [1].

Figure 1. Simple TSA process cycle [1].

The maximum equilibrium loading that can be achieved by a certain cycly will be the different loading n1-n2. The

drawback of TSA over other adsoprtion process such as pressure swing adsorption (PSA) is that it requires longer
[3]
cycle time due to the heating up of the bed for sorbent regeneration . Temperature swing adsorption is more
[4]
efficient for CO2 desorption that pressure swing adsorption (PSA) . Nevertheless, TSA has an advantage of

being environmentally friendly and requires low energy for CO2 capture process [5].

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Temperature Swing Adsorption Process Control for CO2 in Air Capture Using Zeolite as adsorbent

Figure 2. Simple process flow diagram for CO2 capture using temperature swing adsorption [5].

B. Sorbent

In this process, zeolite specifically 13X porous crystalline aluminosilicate is to be used as the solid sorbent

for the CO2 capture in air. This will be used for purification process. The properties of zeolite is being summarized

in the succeeding table.

Table 1. Summary of the properties of 13X Zeolite solid sorbent [1].

Property Value
Shape of particle S,C,P
Size range, US std mesh Various
Internal porosity, % ~38
Bulk dry density, kg/L 0.58-0.64
Average pore diameter, nm 1.0
Surface area, km2/kg ~0.6
Sorptive capacity, kg/kg (dry) 0.25-0.36

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Temperature Swing Adsorption Process Control for CO2 in Air Capture Using Zeolite as adsorbent

Identification and description of process variables and disturbances

A. Process Variables

The process variables in the temperature swing adsorption process are as follows:

CONTROLLED VARIABLES

Adsorption temperature

Desorption temperature

MANIPULATED VARIABLE

Cooling and Heating medium mass flowrates

B. Disturbances

Desorption may occur with the increase in the temperature of the adsorbed solutes.

Large decrease in the temperature may stimulate condensation during the adsorption.

Decrease in the desorption temperature decrease desorptive quantity, CO2 purity and recovery.

Process Dynamics/Models

In order to represent the dynamic model of the process of temperature swing adsorption, some assumptions

and modifications with regards to the diagram are done. First, it is assumed that the boundary of the process where

modelling is done is only limited for the adsorption, heating, desorption or regeneration of the sorbent and the

cooling of the regenerated sorbent. Second, it is assumed that only one stream enters and exits the adsorption

column, while on the other hand for the desorption, only one stream enters and exits the column, disregarding the

effect of the stream of sorbent make-up to the balances. Energy balance is being carried out since the parameter

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Temperature Swing Adsorption Process Control for CO2 in Air Capture Using Zeolite as adsorbent

that is being monitored is the temperature of the stream that enters the adsorption column and the desorption

column, through manipulating the flowrates of the cooling and heating media in both cooler and heater.

Adsorption Column:

For the dynamic model in adsorption, the energy balance starts with the definition of the general energy

balance equation, which accounts the inlet energy, outlet energy, the generated energy and the energy that comes

a reaction (if any), so as to come up with the accumulation rate of energy within the column. This is

mathematically represented in the succeeding equations.

= + (1)

Since, there is no generated energy within the column, and there is no reaction taken place within, therefore the

GEN and RXN terms will just be equal to zero. Equation (1) is being modified as:

= (2)

These energy terms can be represented trhough the enthalpies of the input and output streams.

() (3)
=

Recall, that the enthalpy of such compenent can be also estimated using the sensible heat equation: H = mCp (T-

Tref), where m is the mass flow rate of the stream, Cp is the specific heat and Tref, is the reference temperature,

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Temperature Swing Adsorption Process Control for CO2 in Air Capture Using Zeolite as adsorbent

usually equal to zero. The inlet enthalpy comes from the stream with temperature T1, and the outlet enthalpy

comes from the stream with temperature T2.

() (4)
= 1 2

() (5)
= 1 1 (1 ) 2 2 (2 )

The energy accumulated inside the column is being represented as:

= ( ) (6)

Where is the density fo the fluid, A is the cross-sectional area of the column and z is the column height.

Incorporating (6) to (5), giving us:

( ( )) (7)
= 1 1 (1 ) 2 2 (2 )

In this case, , A, z and Cp can be assumed to be constant for the fluid inside the tank, giving us:

( ) (7)
= 1 1 (1 ) 2 2 (2 )

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Temperature Swing Adsorption Process Control for CO2 in Air Capture Using Zeolite as adsorbent

Since Tref is also equal to zero,

( ) (8)
= 1 1 1 2 2 2

The equation can be modified for a steady-state process, by applying the different assumptions pondered for such

process.

0 = 1 1 1 2 2 2 (9)

In order to transform the equation into the simpler linear equations, the variables included in the equation should

be transformed into deviation variables.

1 = 1 1 (10)

2 = 2 2 (11)

( ) (12)
= 1 1 1 2 2 2

When TTA = T2,

(2 ) (13)
= 1 1 1 2 2 2

By taking the inverse laplace transform of the preceding equation, this gives us:

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Temperature Swing Adsorption Process Control for CO2 in Air Capture Using Zeolite as adsorbent

= 1 1 2 2 (14)

+ 2 2 = 1 1 (15)

( + 2 2 ) = 1 1 (16)

1 1 (17)
=
+ 2 2

1 1 (18)
2 2
=
+1
2 2

1 1
1 =
2 2

1 =
2 2

1 (19)
=
1 + 1

From the energy balance, equation (19) is derived, which represents the transfer function for the adsorption

column.

Desorption Column:

Energy Balance:

= + (1)

= (2)

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Temperature Swing Adsorption Process Control for CO2 in Air Capture Using Zeolite as adsorbent

() (3)
=

() (20)
= 5 6

() (21)
= 5 5 (5 ) 5 5 (5 )

= ( ) (22)

( ) (23)
= 5 5 (5 ) 6 6 (6 )

( ) (24)
= 5 5 5 6 6 6

0 = 5 5 5 6 6 6 (25)

5 = 5 5 (26)

6 = 6 6 (27)

( ) (28)
= 5 5 5 6 6 6

(2 ) (29)
= 5 5 5 6 6 6

= 5 5 6 6 (30)

+ 6 6 = 5 5 (31)

( + 6 6 ) = 5 5 (32)

5 5 (33)
=
+ 6 6

5 5 (34)
6 6
=
+1
6 6

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Temperature Swing Adsorption Process Control for CO2 in Air Capture Using Zeolite as adsorbent

2 =

2 =

2 (35)
=
2 + 1

Therefore, from these balances, equation (35) is the transfer function for the desorption process.

Heater:

For the energy balance in the heater, same procedures were done as for the adsorption and desorption. The

only difference is that the energy inside the heater is in terms of volume, density of the fluid and the specific heat.

Also, the inlet enthalpies are in the sum of the enthalpies of the streams with temperatures T2 and T3. For the

outlet enthalpy, it is the sum of the enthalpies of streams with temperature T4 and T5.

() (36)
= 2 + 3 4 5

The general energy balance equation when required parameters and deviation variables are applied is shown in

the succeeding equation.

( ) (37)
= 2 2 2 3 3 3
5 5 5 4 4 4

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Temperature Swing Adsorption Process Control for CO2 in Air Capture Using Zeolite as adsorbent

The final transfer function for the heater is shown in the succeding equations, as well as the gains and the time

constants.

2 2 3 3 4 4 (38)
5 5 5 5 5 5
= +
+1 +1 +1
5 5 5 5 5 5

3 =

4 =

4 4
5 =

3 =
5 5

3 4 5 (39)
= +
3 + 1 3 + 1 3 + 1

Cooler:

Energy Balance:

() (40)
= 6 + 7 8 1

( ) (41)
= 6 6 6 7 7 7
8 8 8 1 1 1

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Temperature Swing Adsorption Process Control for CO2 in Air Capture Using Zeolite as adsorbent

6 6 7 7 8 8 (42)
1 1 1 1 1 1
= +
+1 +1 +1
1 1 1 1 1 1

6 6
6 =
1 1

7 7
7 =
1 1

8 8
8 =
1 1

4 =
1 1

6 7 8 (43)
= +
4 + 1 4 + 1 4 + 1

Block diagram

Adsorption:

1
=
1 + 1

Desorption:

2
=
2 + 1

Heater:

3 4 5
= +
3 + 1 3 + 1 3 + 1

Cooler:

6 7 8
= +
4 + 1 4 + 1 4 + 1

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Temperature Swing Adsorption Process Control for CO2 in Air Capture Using Zeolite as adsorbent

4 5
3 + 1 3 + 1

1 3 2
1 + 1 3 + 1 2 + 1

6
4 + 1

8
4 + 1

7
4 + 1

Figure 3. Block diagram for the one of the temperature control system.

Control strategy description

A. Temperature control at the adsorption bed inlet from cooler 1 and inlet from the sorbent recycle stream

Temperature in the inlet feed to the adsorption column should be cooled down to the adsorption

temperature inside the column so as to avoid sudden increase or decrease in its values which may possibly cause

either condensation of the adsorbate or desorption of the adsorbed solutes. The control is being done by putting a

thermocouple in the adsorption column, which passes signals through the temperature transmitter in the presence

of electric signals. The signal from the temperature transmitter should now go to the temperature controllers which

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Temperature Swing Adsorption Process Control for CO2 in Air Capture Using Zeolite as adsorbent

then decide whether the control valves of the inlet streams of the cooling medium in the cooler 1 and cooler 2

should be opened or not.

B. Temperature control at the desorption inlet stream from the heater

Temperature of the inlet stream from the heater should has achieved and maintained at the desorption

temperature so as to maximize the desorptive quantity of the process. The control is being done by putting

thermocouple inside the desorption column, which then transmits signals to the temperature transmitter though

electric signals. These signals will now be then trasported to the temperature controller. The controller will make

the final decision whether the control valve of the stream of the heating medium in the heater should open or not.

Instrumentation

The following are the instruments that are used in the system:

Acronym Instrument

TT Temperature transmitter

TC Temperature Controller

Temperature Transmitter

The KOBOLD TSA temperature sensor is suitable for service in applications requiring temperature

monitoring, detection, or regulation of gases or liquids. It responds quickly and operates with fluid temperatures

between -40 and 150 C. The rugged pipe section housing is available in either brass or stainless steel material

with " to 1" female NPT threads. The laser-trimmed electronic sensor generates a strong signal, so no line

compensation is required for supply leads less than 20 meters in length. The available output signals are

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Temperature Swing Adsorption Process Control for CO2 in Air Capture Using Zeolite as adsorbent

compatible with many conventional control and indicating devices. KOBOLD offers a range of transmitters and

displays for further evaluation and processing of the output signal if desired.

Figure 4. Temperature transmitter specifications.

Temperature Controller

The PID controller is the most common form of feedback. It was an essential element of early governors

and it became the standard tool when process control emerged in the 1940s. In process control today, more than

95% of the control loops are of PID type, most loops are actually PI control. PID controllers are today found in

all areas where control is used. The controllers come in many different forms. There are stand-alone systems in

boxes for one or a few loops, which are manufactured by the hundred thousands yearly. PID control is an

important ingredient of a distributed control system. The controllers are also embedded in many special-purpose

control systems. PID control is often combined with logic, sequential functions, selectors, and simple function

blocks to build the complicated automation systems used for energy production, transportation, and

manufacturing. Many sophisticated control strategies, such as model predictive control, are also organized

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Temperature Swing Adsorption Process Control for CO2 in Air Capture Using Zeolite as adsorbent

hierarchically. PID control is used at the lowest level; the multivariable controller gives the setpoints to the

controllers at the lower level. The PID controller can thus be said to be the bread and buttertt of control

engineering. It is an important component in every control engineers tool box.

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Temperature Swing Adsorption Process Control for CO2 in Air Capture Using Zeolite as adsorbent

Piping and instrumentation diagram

The figure below shows the process flow diagram of the temperature swing adsorption for the CO2 capture

using solid sorbent Zeolite. This also includes the control mechanisms done, for maintaining the temperature for

the adsorption and desorption processes. The control of the temperature is done through manipulating the flow of

the entering cooling and heating media in both cooler and heater.

Figure 4. Piping and Instrumentation Diagram for TSA.

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Notes:

TC Temperature Controller

TT Temperature Transmitter

References

[1] Green, D. W. and Perry, R. H. 2008. Perrys chemical engineers handbook. McGraw-Hill Companies Inc.

Eigth Edition.

[2] Khajuria, H. 2011. Model-based Design, Operation and Control of Pressure Swing Adsorption System.

Center for Process System Engineering, Department of Chemical Engineering, Imperial College Londo, United

Kingdom.

[3] Thambimuthu, K., Soltanieh, M. and Abanades, J. C. 2005. IPCC Special Report on Carbon Dioxide

Capture and Storage, Capture of CO2. Intergovernmental Panel on Climate Change.

[4] Garcia, S., Gil, M. V., Pis, J. J., Rubiera, F. and Pevida, C. 2012. Cyclic operation of a fixed-bed pressure

and temperature swing process for CO2 capture: Experimental and statistical analysis. Elsevier Ltd. International

Journal of Greenhouse Gas Control, Volume 12, 35-43.

[5] Bell, D. A., Towler, B. F. and Fan, M. 2010. Coal Gasification and Its Applications. William Andrew,

Elsevier Ltd.

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