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

Abou-Rayyah

Report 1: Model & Assumptions

UNIT 3 : CO2 REMOVAL COLUMN (MOHD SAID, NORAKMAR) -- DATA PAGE

Operating data External Diameter (m) Height (m) Design pressure (atm) Operating pressure (atm) Position Design temperature (C) Operating temperature (C) Internal Number of trays Tray spacing Feed stages (counted frm top) Packing type Packing diameter (mm)
Figure 3.1: Unit 3 Process Schematic Table 3.1: Unit 3 Operating data

2.4 3.6 1.1 1.0 Top 77.2 70.2 Bottom 52.6 47.8

4 0.5 Stage 1 (Stream 6) Stage 4 (Stream 3) Ceramic Raschig rings 50

Stream No. 3 6 7 124000 380677 153634 Mass Flowrate (kg/hr) o 130.0 96.7 70.2 Temperature ( C) 1 1 1 Pressure (atm) 1 0 1 Vapor Fraction 223030 -4449100 -192930 Enthalpy (MJ/h) Component Weight Fractions 0.020 0.000 0.000 CO2 0.980 0.000 0.791 Ethylene 0.000 0.671 0.209 Water 0.000 0.329 0.000 MDEA
Table 3.2: Unit 3 Stream Data

8 351042 47.8 1 0 -4041000 0.007 0.000 0.636 0.357

Required Specification

Achieved Specification

No specifications required

Table 3.3: Unit 3 Specifications

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

Report 1: Model & Assumptions

Unit Description
This unit is to remove CO2 from the recycle gas stream containing ethylene to reduce the CO2 buildup circulating in the system. The presence of CO2 in the recycle gas stream into the reactor will also reduce the conversion rate and thus production of VAM. The removal will also ensure a lower throughput of materials which can improve the subsequent unit design. 30% Methyl diethanolamine (MDEA) and 70% water are used as the solvent (Alie, C.F., 2004) to remove the CO2 via absorption. Due to the corrosive nature of MDEA, this column will utilize Raschig Rings as packing.

Assumptions
1. Perfect mixing on each tray. Acceptable due to relatively small volume of tray. 2. Thermodynamic equilibrium between liquid and vapour on tray i.e. Murphree efficiency of 1. Including the Murphree equation in the model is relatively simple but estimating the efficiencies accurately is difficult. 3. Negligible vapour molar and energy holdup. Since the operating pressure is low (1atm), the smaller vapour density would result in a much smaller molar/energy holdup compared to the liquid molar/energy holdup. 4. 3-component mixture (CO2, ethylene, water). Acceptable as the solvent is 70% MDEA and 30% water. A multicomponent separation is more complicated to model. 5. Adiabatic column operations due to good column insulation 6. Constant pressure throughout column for simplification. 7. Fixed volume for each stage due to limited data on the geometry. 8. Lumped system. Concentration variation within a single stage is negligible. 9. No downcomer dynamics, entrainment, weeping or flooding due to a sound column construction and satisfactory operating conditions (i.e. suitable liquid and vapour feed flowrates). It is also difficult to know what is going on inside the column regarding these problems to model them accurately. Furthermore, at steady-state, the separation is not notably affected by them. 10. Steady-state operations as it is assumed to undergo continuous operation and the model is at equilibrium so there will be no generations. 11. Constant equimolar vapour overflow for all stages except the feed stage. Attributed to the nearly equal molar heats of vaporization of the components. Thus, for each mole of vapour condensed, sufficient heat is released to vaporize one mole of liquid. 12. Linear tray hydraulics were included as the liquid flowrate leaving a tray depends on the varying liquid molar holdup on each tray which is bubbling away. Using this, a linear relationship between the outlet liquid flowrate and the tray molar holdup can be added to the model. 13. Negligible chemical reaction between CO2 and MDEA for simplification of model. 14. Negligible kinetic and potential energy as relatively much smaller than internal energy. 15. Zero heat of mixing as it is relatively much smaller than the heat of vaporisation so there is no major impact on the energy balance.

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

Report 1: Model & Assumptions

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

Report 1: Model & Assumptions

Model Development & Degree of Freedom Analysis

Table 3.4: Dynamic models, number of equations and number of variables in a degrees of freedom analysis

The physical properties model will calculate the Henry coefficients, liquid and vapour molar enthalpies and molar fractions which are then propagated into the tray model. The tray model will calculate the liquid and vapour outlet flowrates. The sump tank model represents the tank at the bottom of the absorption column to be used for control purposes. Eqn no 3.1 3.2 3.3 3.4 Henrys Law Henry coefficients as function of temperature Sum of mole fractions Component liquid enthalpy Equation Physical Properties Model (PP) ( ) ( ( 3.10 3.11 3.12 3.13 3.14 Component vapour enthalpy Component heat of vaporisation Reduced temperature Liquid enthalpy leaving tray Vapour enthalpy leaving tray Tray Model (Tray) 3.4 3.5 3.6 3.7 3.8 Component molar balance Component molar holdup Total molar holdup Equimolar vapour overflow Linear tray hydraulics NC NC 1 1 1 3NC+4 1 0 0 0 ( ) ) ( ) ( ) ( ) NC NC NC 1 1 2NC NC 0 1 1 ) ( ) NC-1 NC 1 NC yi , xi , T 3NC 1 0 NC No. equations New variables No. variables

( )

J. Olayiwola, T. Udabor, N. Mohd Said, R. Lazar, M.Shahabudin, M.Abou-Rayyah Liquid height on tray Energy balance Internal energy Total

Report 1: Model & Assumptions

3.15 3.16

1 1 1 8NC+8

1 3 0 10NC+12

Degree of Freedom = 2NC + 4

Sump Tank Model (SumpTank) 3.1 3.2 3.3 Component molar balance Component molar holdup Total molar holdup Liquid height in tank Total NC NC 1 1 2NC+2 3NC+2 1 0 1 3NC+4

Degree of Freedom = NC+2

The two following models are used to calculate the liquid enthalpy coming into Tray 1 (top tray) ,

and vapour enthalpy coming into the bottom tray,

Inlet Liquid Enthalpy Model (PPLin) Eqn no 3.9 Description Component liquid enthalpy entering column at Tray 1 ( ( ( 3.13 Total liquid enthalpy entering column at top Total ) ) ) 1 NC+1 1 NC+2 Equation ( ( ) ) No. equations NC New variables No. variables NC+1

Degree of Freedom = 1 (Tlin)

Inlet Vapour Enthalpy Model (PPVin)

J. Olayiwola, T. Udabor, N. Mohd Said, R. Lazar, M.Shahabudin, M.Abou-Rayyah 3.9 Component liquid enthalpy entering column at bottom tray ( ( )

Report 1: Model & Assumptions

) ( )

( (

) )

NC

NC +1

3.10

Component vapour enthalpy entering column at bottom tray

NC

2NC

3.11 3.12 3.13 3.14

Component heat of vaporisation at bottom tray Component reduced temperature at bottom tray (gas inlet) Total liquid enthalpy entering column at the bottom Total vapour enthalpy entering column at the bottom Total

NC NC -

NC 0 1 1 4NC + 3

1 1 3NC +2

Degree of Freedom = NC +1 Overall D.O.F = NC + 2

Temperature of the liquid and gas feed coming into the column, and and the liquid molar fractions in the gas feed (zero as gas feed is 100% vapour) were chosen to be specified for these two models as they are available and given as a specification. This is more feasible rather than specifying the gas and liquid enthalpies going into the column as these enthalpy values are obtained from CHEMCAD and the software might have used a different reference temperature, thermodynamic model or units.

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

Report 1: Model & Assumptions

The column section model links the Tray model to the Sump Tank Model. Variables in the jth Tray are identified using the subscript [j] , variables in the Sump Tank are identified using the subscript [ST]. The inlet liquid and vapour enthalpies coming into the column take the values calculated by the PPLin and PPVin models.
Table 3.5: Column models, number of equations and number of variables in a degrees of freedom analysis

Column Model Submodel Tray Eqn 3.17 3.18 Equation Linking liquid flowrates & liquid enthalpies Linking vapour flowrates & vapour enthalpies Linking liquid molar fractions Linking vapour molar fractions Linking Tray 1s inlet liquid enthalpy to value calculated by PPLin model Linking bottom trays inlet vapour enthalpy to the value calculated by PPVin model Total Submodel Sump Tank Eqn 3.21 3.22 Equation Linking bottom tray outlet liquid flow to tank inlet Linking bottom tray outlet liquid molar fractions to tank inlet 1 NC Degree of Freedom 2NC + 4 No. equations 2(NT-1) 2(NT-1) No Submodel NT New variables 0 0 Total Degree of Freedom (2NC +4) NT No. variables

3.19 3.20

(NT-1)NC (NT-1)NC 1 1

0 0 0 0

4(NT-1) + 2NC (NT-1) + 2

(2NC + 4) NT No Submodel 1 New variables 0 0 Total Degree of Freedom NC +2 No. variables

Degree of Freedom = 2NC + 2

Degree of Freedom NC + 2 No. equations

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

Report 1: Model & Assumptions

NC+1

NC +2

Degree of Freedom = 1 Overall Degree of Freedom for Model :

From the analysis, 2NC + 3 variables need to be specified. The variables specification or can be obtained directly from ChemCAD. , , and and

2NC+3

are chosen as they are feasible and either provided as

Closed-Loop In the closed loop analysis, a Level Controller (PI) model and a Ratio Controller (P) model are added to the Column Model for the Basic Process Control simulation. Level Controller Model 3.4 3.5 3.6 3.7 Error calculation Integral error calculation Control action Capping liquid flowrate out of column via tank Total { ( ( ) 4 4 ( ) ( ) ) 1 1 1 1 2 1 1 0

Degree of Freedom = 0
For this model, the measured height, h takes the value of the liquid height in the Sump Tank, h ST. The liquid outlet flowrate of the Sump Tank, LoutST is now controlled instead of assigned and takes the value of the calculated liquid flowrate of the level controller , LoutLC.

Ratio Controller Model 3.9 3.10 3.12 3.13 3.11 Set-point liquid feed inlet flowrate Error Control signal Capping control signal Liquid flowrate into column Total ( { ( ( ) ) ) 1 1 1 1 1 5 2 1 1 0 1 5

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

Report 1: Model & Assumptions

Degree of Freedom = 0
For this model, the measured gas inlet flowrate, VinRC is linked to the vapour flowrate coming into the bottom tray of the column, Vin NT. The liquid inlet flowrate of Tray 1, Lin1 is now controlled instead of assigned and takes the value of the calculated liquid flowrate of the ratio controller , Lout RC. Thus, overall, the total degrees of freedom of the controlled column is still 2NC + 3. The variables , , ,, and are specified while and are now controlled. For the Safety Control simulation, an ESDV model was added to the column model to represent an emergency shutdown valve switch loop. ESDV Model 3.9 Liquid flowrate into column 1 3.10 Valve position and gas inlet flowrate based on 2 { height measurement { Total 3 6

3 3

Degree of Freedom = 1 (Lin and hmax)

The measured height, h takes the value of the liquid height in the Sump Tank, hST. Lin1 and VinNT to column will now be controlled instead of assigned by ESDVs LoutESDV and VinESDV. Thus, the overall degrees of freedom is 2NC+4. The maximum liquid height, hmaxESDV, initial valve position, valveESDV, inlet liquid and gas molar fractions, , from the Column Model will be specified in the process, reducing the degrees of freedom to 0.

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

Report 1: Model & Assumptions

Discussion
Summary: Assumptions were made when developing the mathematical models above for the unit dynamic operation which can affect its accuracy to a certain extent as discussed below. Some of the assumptions used may have a minor effect on the results, for examp le the level of separation could be affected by the use of Henrys Law. However, Henrys law provides a good approximation of solubility, and is dependent on temperature, meaning changes in te mperature will be accounted for, which will be vital when it comes to considering the closed-loop response. The packed column is modelled as a tray column with linear hydraulics to reduce the complication of the model and the loss of accuracy is negligible (Ref). Linear tray hydraulics relate the liquid flowrate leaving a tray to the liquid molar holdup. Using this, disturbances in the feed flowrates and its effects on the column behaviour (holdup and flowrate-wise) can be modelled for control purposes. Equivalent relationships for packed columns can be obtained via ____ but again, extra computational effort is needed which is why the column will just be modelled as a tray column. Perfect mixing is assumed to simplify the model. Although the simulation results would be less accurate, a distributed model would have to be used otherwise which will increase the computational costs. Mass transfer limitations may also affect the separation as it was not taken into account. The reaction between CO2 and MDEA was also disregarded to simplify the model as a rate-based model would be needed to model the boundary layers (liquid and gas film) and there is heat of reaction associated with the process. By ignoring the reaction, this heat of reaction wont be included in the energy balance. In reality, this reaction i s exothermic (Ref) and the temperature on the trays might actually be higher than predicted by the simulation. If the reaction is particularly exothermic, this might severely underpredict the temperatures and a runaway exothermic reaction might occur. However, since the heat of reaction between CO2 and MDEA is relatively small (kJ) this assumption holds for this process and will not affect its safety. Weeping, flooding and entrainment are disregarded due to sound column construction and satisfactory operating conditions (i.e. suitable liquid and vapour feed flowrates). However, this would mean in cases of failure, the column response and behaviour cannot be predicted which can lead to a major accident. This assumption also defeats the main purpose of dynamic simulations which is to maintain the column safety. Nevertheless, since this project focuses a dynamic operation close to the nominal steady state far from extreme conditions such as weeping and flooding, this assumption is acceptable and will not jeopardise the column safety. Vapour molar holdup is neglected which is acceptable for the units operating pressure. However, if the column requires a hig her operating pressure in the future, the model will be not be accurate so this limits the units operating pressure range. Equimolar vapour overflow entails an instantaneous change in vapour flowr ates in the column which is not plausible for large-capacity columns. Thus, further analysis of the results may be required. An energy balance was added and Henrys constant in this model is temperature-dependent which will make the model more accurate as it will take into account the differences in temperature throughout the column. The heat of mixing was assumed to be zero as it is much smaller than the heat of vaporisation so there will be no major impact on the energy balance. Adiabatic operation was assumed but in reality, a certain amount of heat is lost to the surroundings, which will affect the energy balance term and subsequently the temperature and Henry constants which determine the separation of the mixture. However, good insulation of the column can reduce this heat loss to a negligible amount.

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

Report 1: Model & Assumptions

Constant pressure was also assumed which can lead to difficulties in pressure controls as any changes in the column pressure will not be accounted for in the simulation. Thus, when designing the controls, another variable that can indicate the pressure level should be measured instead for the safety control such as the gas inlet flowrate for example. Thus, when this variable exceeds the maximum value for the column (which can be calculated from a correlation with the pressure or from experiments), the safety control can be activated in the simulation. A lumped system was also assumed but in reality there will always be a variation of concentration within a stage. This might affect the component molar fractions on the trays. However, extra computational effort has to be implemented which will increase the cost to obtain this extra accuracy. Although equilibrium is rarely achieved on a tray and including the Murphree equation in the model is relatively simple, estimating the efficiencies accurately is difficult. Thus, Murphree efficiency of 1 was assumed. Besides, a different hydrodynamic behaviour will be displayed if Murphree efficiencies are used because the number of equilibrium and actual trays will be different even though the same separation is attained. Overall, there will be inevitable inaccuracies in the results obtained but they should remain within an acceptable range and display the correct trend as long as the unit operates close to nominal steady-state and undergoes small disturbances. However, this limits the column operating range and disturbances range. If a large disturbance occurs, the column model might not be sufficient to simulate the column response. Nevertheless, at the moment, the model is deemed satisfactory for the unit operation and can provide an adequate composition and temperature profile throughout the column. No 1 Assumption Packed column modelled as tray column Justification The mass transfer model for a packed column is more computationally intensive and relies heavily on empirical equations for properties such as diffusivity, mass transfer coefficients and interfacial area. Simplification as including mass transfer equations will make the model very complex. Henrys Law can be assumed to be responsible for all mass transfer action (See Assumption ). Simple models also tend to provide reasonably accurate results for relatively little work. Lower cost Trays are much better for handling solids and fouling applications, offer greater residence time for slow absorption reactions, can better handle high L/G ratios and intermediate cooling, give better liquid turndown, and are more robust and less prone to reliability issues such as those resulting from poor distribution. Another reason is that the simple models often tend to provide Relatively small volume of tray (2.26 m3 as obtained from CHEMCAD). If volume is bigger than ~5m3 this assumption wont be very accurate . The ideal stage model is relatively simple, but requires an overall

Perfect mixing on each tray. (limit)

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

Report 1: Model & Assumptions

efficiency for trays or a height equivalent of a theoretical stage for packing. The mass transfer model is significantly more computationally intensive and relies heavily on empirical equations for properties such as diffusivity, mass transfer coefficients and interfacial area. http://www.bre.com/portals/0/technicalarticles/Comparison%20of%2 0Models.pdf Rate-based equations would have to be used to accurately describe changes from liquid bulk to outlet, and would be too complex for this report. For nonreactive systems with cross-flow trays, the concentration varies across the tray as a result of nonideal mixing. In the limit of perfect liquid mixing on the tray, the concentration is constant across the tray and the point efficiency and tray efficiency are the same. For nonideal mixing, concentration gradients develop across the tray that lead to differences in the tray and point efficiencies. In the extreme limit of plug flow across the tray, the concentration gradient is maximized and the difference is also at a maximum. 3 Solubility and all mass transfer described by Henrys Law. Henrys Law gives good concentration approximations to experimental data. Low operating pressure (Henrys Law does not work for gases at high pressures) Petrucci, Ralph, and William Harwood. F. Geoffrey Herring. Jeffry Madura. General Chemistry: Principles and Modern Applications. 9th ed. Upper Saddle River, NJ: Pearson, 2007. Henrys Law accounts for all mass transfer. Including the Murphree equation in the model is relatively simple but estimating the efficiencies accurately is difficult.

Thermodynamic equilibrium between liquid and vapour on tray i.e. Murphree efficiency of 1. Negligible vapour molar and energy holdup.

Since the operating pressure is low (1atm), the smaller vapour density would result in a much smaller molar/energy holdup compared to the liquid molar/energy holdup due to the smaller number of moles contained within the vapour volume (Jana, 2005)

J. Olayiwola, T. Udabor, N. Mohd Said, R. Lazar, M.Shahabudin, M.Abou-Rayyah 6 3-component mixture (CO2, ethylene, water). Adiabatic column operations Constant pressure throughout column Constant liquid density

Report 1: Model & Assumptions

7 8

Acceptable as the solvent is 70% water and 30% MDEA. Pseudocomponent values are used wherever possible which is obtained from ChemCAD (average density, average molar weight). Due to good column insulation therefore negligible heat losses. Column is operating at atmospheric pressure and the pressure drop across column obtained from ChemCAD simulation is very small ( 0.0048bar - 0.47% of operating pressure ) thus negligible As there is only a small change in temperature, the liquid density of the components is unlikely to vary significantly. From CHEMCAD, the maximum density variation between the trays are only 0.51% Due to limited data on the geometry Concentration variation within a single stage is negligible due to perfect mixing assumption (justify). Due to a sound column construction and satisfactory operating conditions (i.e. suitable liquid and vapour feed flowrates). It is also difficult to know what is going on inside the column regarding these problems to model them accurately. Negligible heat of solution Liquid flowrate leaving a tray depends on the varying liquid molar holdup on each tray which is bubbling away. Using this, a linear relationship between the outlet liquid flowrate and the tray molar holdup can be added to the model. The liquid hydraulics are also very important in predicting the columns dynamic performance (Jana, 2005) For simplification of model. Henrys law is responsible for all mass transfer Relatively much smaller than internal energy which dominates the energy balance equation.

10 11

Fixed volume for each stage Lumped system.

12

No downcomer dynamics, entrainment, weeping or flooding

13 14

Constant equimolar vapour overflow Linear tray hydraulics were included

15

Negligible chemical reaction between CO2 and MDEA Negligible changes in kinetic and potential energy

16

J. Olayiwola, T. Udabor, N. Mohd Said, R. Lazar, M.Shahabudin, M.Abou-Rayyah 17 18 Zero heat of mixing (value) Gases behave ideally

Report 1: Model & Assumptions

Ideal solution. The value is relatively much smaller than the heat of vaporisation so there is no major impact on the energy balance. Reasonably high operating temperature and low pressure (97C and 1 atm)

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

Report 1: Model & Assumptions

Model Development & Degree of FreedomAnalysis

Table 3.4: Dynamic models, number of equations and number of variables in a degrees of freedom analysis

Eqn no 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 3.9 3.10 3.11 3.12 3.13 3.14 3.15 3.16 Total ( )

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

No. equations NC-1 NC 1 NC NC 1 1 1

New variables

No. variables

yi , xi , Hi T -

3NC 1 0 3NC+4 1 0 0 0 NC 2NC NC

( ( ) ) ( ) ( ) ( ) ( )

NC NC NC NC 1 1 1 1 8NC+7 -

0 1 1 3 0 10NC + 11

Degree of Freedom = 2NC + 4

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

Report 1: Model & Assumptions

VLE Model: Eqn (3.1) is the Henrys expression for the VLE equilibrium on each tray. Eqn (3.2) will determine how the Henrys constant will vary with temperature, assuming adiabatic operation and Eqn (3.3) is to ensure the total vapour molar fractions are 1. Tray Model: Eqn (3.4) is the component molar balance of the components on each tray, neglecting the chemical reaction between CO 2 and MDEA. Eqn (3.5) and (3.6) are to ensure the total molar holdup is the sum of all components molar holdup, assuming negligible vapour holdup. Eqn (3.7) describes the vapour flowrate throughout each tray, assuming constant equimolar overflow. Eqn (3.8) is the linear tray hydraulics for the liquid flowrate throughout each tray, assuming a linear relationship between the molar holdup and the liquid flowrate leaving the tray. It also assumes no dynamics in the downcomer, no weeping, flooding or entrainment. Eqn (3.9) and (3.10) describe the liquid and vapour molar enthalpy of the components, again assuming no reaction and also negligible heat of mixing. Eqn (3.11) describes the heat of vaporisation for each component. Eqn (3.12) is to calculate the reduced temperature to be used in Eqn (3.11). Eqns (3.13) and (3.14) are to ensure the total liquid and vapour enthalpies are the sum of that of the components. Eqn (3.15) is the tray energy balance and Eqn (3.16) is the tray energy holdup, assuming adiabatic operation, no reaction and negligible kinetic and potential energy.
Table 3.5: Column models, number of equations and number of variables in a degrees of freedom analysis

Submodel Tray Eqn no 3.17 3.18 3.19 3.20 3.21 3.22 Equation NT-1 NT-1

Column Model Degree of Freedom 2NC + 4 No. equations -

No Submodel NT New variables 0 0 0 0 0 0

Total Degree of Freedom (2NC +4) NT No. variables

(NT-1)NC (NT-1)NC NT-1 NT-1 4(NT-1) + 2NC (NT-1)

(2NC + 4) NT

Degree of Freedom = 2NC + 4

From the analysis, 2NC + 4 variables need to be specified. The variables obtain. , , and and and are chosen as they are practical, feasible and easy to

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

Report 1: Model & Assumptions