4 UNIT 4 : CO2 SOLVENT RECOVERY COLUMN (LAZAR, ROUVIN) -- DATA PAGE Operating data External Diameter (m) Height

(m) Design pressure (atm) Operating pressure (atm) Internal Number of Stages Packing Type 1.37 2.7 1.10 1.21 3 Ceramic Raschig Rings 50 1 3 2.7

Packing Diameter (mm) Stream 8 Feed Stage (from top ) Stream 9 Feed Stage (from top) Height (m)
Table X: Unit 4 Op Data

Figure X: Unit 4 Process Schematic

Stream No. Mass Flowrate (kg/hr) Temperature (oC) Pressure (bar) Vapor Fraction Enthalpy (MJ/h) CO2 Ethylene Water MDEA

8 9 10 11 351042 37875 10588 355676 47.8 150.0 98.3 101.7 1 4 1 1 0 1 1 0 -4041000 -501090 -129490 -414180 Component Weight Fraction 0.007 0.000 0.234 0.000 0.000 0.000 0.002 0.000 0.636 1.000 0.763 0.669 0.357 0.000 0.001 0.331
Table X: Stream Data for Unit 4

21 378330 101.7 4 0 -4412600 0.000 0.000 0.669 0.331

22 22703 101.7 1 0 -264370 0.000 0.000 0.669 0.331

Required Specification for Stream 10

99.5% of CO2 Removed from Stream 22 99.9% of CO3 Removed

Achieved Specification for Stream 10

Table X: Specification for Unit 4

Unit Description
The purpose of this absorption unit is to recover the methyl diethanolamine (MDEA) solvent used in the previous absorption column (Unit 3) in order to recycle it back into that column so as to essentially prevent wastage and reduce costs and to also ensure that the CO2 removed in the previous column meets the required specification. Steam has been chosen as a suitable stripping solvent (Stewart and Lanning, 1994) to remove the MDEA via absorption. The amount of steam used in the inlet stream (Stream 9), as shown in Table X, was determined by utilizing the Steam Rate Rule of 0.12 kg of Steam for every 1 litre of MDEA (Kohl and Nielsen, 1997). Due to the corrosive nature of MDEA, this column will utilize Ceramic Raschig Rings as packing. In addition to that, a purge of 6% of the MDEA/Water recycle has been utilized in order to prevent any build-up of the solvent.

Assumptions
1. Multicomponent mixture (comprising CO2, MDEA and water; since ethylene is present in
such a minute amount in this column, it will be ignored), solubility of which adheres to Henrys Law. 2. Perfect mixing on each tray (i.e. mole fractions on the tray are equal to mole fractions leaving the tray (yi = yiout). 3. This stripping column is modeled as a tray column (i.e. sections of packing correspond to each stage). 4. Internal Energy is considered while kinetic and potential energy are both assumed to be negligible. 5. Column operates adiabatically (i.e. heat loss is negligible as the column is well insulated) 6. Downcomer dynamics are ignored. 7. There is no entrainment, weeping or flooding. 8. No feed to each stage (i.e. feed is entering at the top and bottom of the column). 9. Constant Column Volume and Pressure. 10. Constant Tray Liquid Holdup. 11. Negligible Vapour and Energy Holdup on Tray. 12. Column operates at steady-state(i.e. no generation) and there is no vapour or liquid accumulation. 13. Linear tray hydraulics. 14. All trays modelled in the column are identical (i.e. values of , and are the same in each tray). 15. Thermodynamic equilibrium between liquid and vapour phases (i.e. Murphree efficiency = 1). 16. Equimolar Overflow: The molar vapour flow rate from one stage is equal to the molar vapour flow rate of the stage below (i.e. Vin = Vout). 17. No corrosion or fouling occurs within the column.

Degree of Freedom Analysis

Table 4.4: Dynamic models, number of equations and number of variables in a degrees of freedom analysis

Eqn no 4.1 4.2 4.3

Equation Vapour-Liquid Equilibrium Model ( ) Tray Model ( )

No. equations NC NC 1

New variables

No. variables

yi , xi , Hi T -

3NC 1 0

4.4 4.5 4.6 4.7 4.8 4.9 4.10 4.11 4.12 4.13 4.14 4.15 ( ) (

NC 1 1

3NC+4 0 1

( )

) ( ) ( ) ( ) ( )

NC 1 NC NC NC NC 1

0 0 NC 2NC NC

0 1

4.16 Total

1 8NC+7

0 10NC + 11

Degree of Freedom = 2NC + 3

VLE Model: Henrys Law for the VLE equilibrium relationship is described by Eqn (4.1) and is based on the assumption that the multicomponent mixture adheres to Henrys Law. Assuming temperature dependency, Eqn (4.2) will determine how the Henrys constants will vary at different temperatures.

Tray Model: The component mole balance for each tray is represented by Eqn (4.4), while, assuming negligible vapour holdup, the total molar holdup as the sum of all components is represented by Eqn (4.5) and (4.6). Assuming constant equimolar overflow, Eqn (4.7) represents the vapour flowrate throughout each tray. Assuming a linear relationship between molar holdup and the liquid flowrate from the tray, as well as the absence of downcomer dynamics, weeping, flooding and entrainment, Eqn (4.8) has been derived to represent linear tray hydraulics for each tray. Assuming no reaction occurs in the column and negligible heat of mixing, Eqn (4.9) and (4.10) represent the component liquid and vapour molar enthalpy. Eqn (4.11) represents the component heat of vaporisation while the reduced temperature is described by Eqn (4.12). The sum of liquid and vapour enthalpies is represented by Eqn (4.13) and (4.14). Assuming adiabatic operating conditions, negligible kinetic and potential energy and no reaction, the energy balance for each tray is represented by Eqn (4.15) while the tray energy holdup is represented by Eqn (4.16).

Submodel Tray Eqn no 4.17 4.18 4.19 4.20 4.21 4.22 Equation

Column Model Degree of Freedom 2NC + 3 No. equations NT-1 NT-1 (NT-1)NC (NT-1)NC NT-1 NT-1 4(NT-1) + 2NC (NT-1)

No Submodel NT New variables -

Total Degree of Freedom (2NC + 3) NT No. variables 0 0 0 0 0 0 (2NC + 3) NT

Degree of Freedom = 2NC + 3

Column Model: Eqns (4.17) to (4.11) have been stated in order to link the different properties between the stages.

J. Olayiwola, T. Udabor, N. Mohd Said, R. Lazar, M.Shahabudin, M.Abou-Rayyah

Report 1: Model & Assumptions

Discussion
With regards to the Assumption 3 that states this stripping column will be modelled as an equilibrium tray column as well as Assumptions 2 and 17, it should be said that this was done to avoid the complexities associated with developing a rate-based model; this column is generally considered to be a reactive absorption column (the reaction between CO2 and MDEA is assumed to be instantaneous because of the high temperature of the column (Noorlisa, H, 2011)) and the chemical reactions would affect both the equilibrium relationships as well as rate of absorption. This fact also questions the validity of Assumption 13, as there would be generation in a rate-based model. Furthermore, (Lawal, A. et al., 2009) determined that a rate-based model is a more accurate representation of this unit. As such, eventhough adhering to these assumptions would be relatively inaccurate, they are necessary as developing a more accurate rate-based model would require unavailable information such as column configuration in order to calculate parameters such as interfacial area and heat transfer coefficients (Noorlisa, H, 2011). With reference to Assumptions 7 and 8, entrainment, weeping and flooding as well as downcomer dynamics would influence the flowrates and liquid holdup on each tray. However, eventhough realistic, modelling these phenomena would be too complex. These assumptions also tie in with Assumption 4; this assumption ensures that the input and output (both liquid and vapour phases) of each tray remain constant, which is unrealistic since these properties are prone to disturbances within the column. With regards to Assumptions 6 and 16, assuming adiabatic operating conditions is unrealistic as even utilizing insulation would not completely ensure that there is no heat loss to the surroundings. Also, assuming a Murphree efficiency of 1 is unrealistic because, ultimately, even if they achieve a similar separation, the number of equilibrium stages will generally exhibit different hydrodynamic behaviour to real trays, which would affect many properties in the model such as liquid holdup, flowrates and density of the components leaving the tray. Since this column operates at a low pressure (1 atm), Assumption 12 is fair as a low pressure means there would be low vapour molar density which ensures negligible vapour holdup compared to liquid holdup. Assumption 10, which states that the column operates at constant pressure is somewhat unrealistic; in reality the pressure drop between the trays drives the vapour flow between trays. With reference to Assumptions 14 and 15, these are fair assumptions as they allow the columns behaviour towards disturbances to the feed to be modelled (e.g. liquid tray holdup would change should there be a change in the feed). Taking all of this into account, the validity of this model is dubious as it depicts a somewhat simplistic representation of a stripping column. However, keeping all the complexities associated with a more accurate rate-based model in mind, it should suffice for the purposes of this report.

CONCLUSION
In conclusion, we have successfully developed mathematical models for our distillation and absorption columns based on our key modeling assumptions, which have also been justified. These units (as seen in Figure X: Plant Flowsheet) include an Acetic Acid Scrubber, Acetic Acid Recovery Column, CO2 Removal Column, MDEA Solvent Recovery Column, Light Ends Distillation Column and Heavy Ends Distillation Column. Additionally, degree of freedom analyses have been successfully carried out for each unit and, in turn, we have specified the required number of parameters. As such, our models have been determined to be well-posed in that regard. Each unit section also contains a comprehensive discussion in order to properly explain the effects of our assumptions have on the behaviour as well as overall validity of our developed models. Overall, it can be seen that the mathematical models for each unit are fairly accurate, eventhough some assumptions may be relatively unrealistic, and will allow us to analyse the open loop and closed loop dynamics of each unit in the subsequent stages of this project.

References 1. Stewart, E. J. and Lanning, R.A., Reduce Amine Plant Solvent Losses, Part 2, Hydrocarbon Processing, June 1994, pp. 189. 2. Kohl, A.L. and Nielsen, R.B., Gas Purification, 5th Ed., Gulf Publishing, Houston, Texas, 1997, pp. 150. 3. Noorlisa, H., Dynamic Simulation of MEA Absorption Processes for CO2 Capture from Fossil Fuel Power Plant, Energy Procedia, 2011, 4, pp. 1478. 4. Lawal, A., Wang, M., Stephenson, P., and Yeung, H., Dynamic modelling of CO2 absorption for post combustion capture in coal-fired power plants, Fuel, 88(12), 2009, pp. 2455-2462.