Aspen Plus

Aspen Plus Ethylene Glycol Plant Example

Version Number: V10
May 2017
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Contents
1 Background ..........................................................................................................5

2 Physical Properties...............................................................................................7

3 Reactor Model ....................................................................................................11

4 Evaporator .........................................................................................................13

5 Separation Train.................................................................................................15

6 Overview & Model Applications ..........................................................................19

7 Citations.............................................................................................................21

Contents iii
iv Contents
1 Background

Ethylene glycol (EG) is produced from ethylene oxide reacting with water. EG
has several commercial uses – antifreeze for automobiles, a coolant or heat
transfer agent, or as a raw material for the production of various polyesters
(e.g. polyethylene terephthalate [PET]).
In a complex producing EG, there are three essential process steps: reaction,
drying/evaporation, and separation. Data regression with the new Cubic Plus
Association (CPA) equation of state was used to calculate accurate physical
properties for the glycol system.
In the reaction step, ethylene oxide (EO) and water (H2O) react to form
monoethylene glycol (MEG). Excess EO reacts with MEG to form diethylene
glycol (DEG). This reacts again with EO to form triethylene glycol (TEG),
which reacts again with EO to form tetraethylene glycol (4EG). In this case,
these four glycols will be considered the primary products and heavier glycols
will be ignored.
In the evaporation step, excess water from the reaction step is removed from
the process stream and recycled back to the EG reactor. More than 90 wt%
of water is removed from the process stream to allow for effective separation
of glycols downstream. A triple-effect evaporator is used which utilizes the
heat from steam to evaporate process water in a series of vessels (3 in this
case) with sequential reductions in pressure.
In the separation step, >99.9 wt% of the remaining water is evaporated in a
dehydration column. Downstream, a series of glycol columns yield 3 primary
desired products: MEG, DEG, and TEG. The first column separates MEG from
heavier glycols, with nearly pure MEG removed in the distillate. Downstream
of these columns, the DEG column yields nearly pure DEG in the distillate and
the TEG column yields nearly pure TEG in the distillate.

Figure 1: Aspen Plus flowsheet for an ethylene glycol production process

Contents1 Background 5
6 1 Background
2 Physical Properties

The Cubic-Plus-Association (CPA) equation of state (EOS) was used to

accurately regress the binary interaction parameters for the glycol system.
All of the components in the simulation are conventional and include the
primary reactants and products. Trace components which may be present in
the actual process stream are ignored. The simulation component set is as
follows:
Component ID Type Component name Alias

H2O Conventional WATER H2O

EO Conventional ETYLENE-OXIDE C2H4O-2
MEG Conventional ETHYLENE-GLYCOL C2H6O2
DEG Conventional DIETHYLENE-GLYCOL C4H10O3
TEG Conventional TRIETHYLENE-GLYCOL C6H14O4
4EG Conventional TETRAETHYLENE-GLYCOL C8H18O5

Physical properties for glycol systems (specifically for ethylene glycols and
water) are notoriously difficult to represent by most out-of-box physical
property methods, such as Peng-Robinson (PR) EOS or Predictive Soave-
Redlich-Kwong (PSRK) EOS. In fact, CPA includes the cubic function from
PSRK plus the Statistical Association Fluid Theory (SAFT) association term.
Data regression was used to determine the Kij and Vij terms in the equation of
state model. The Kij term is the basis for the cubic function:

where

The Kij and Vij values were regressed against experimental data sets from the
National Institute of Standards and Technology (NIST) database directly from
within Aspen Plus. With data regression and the CPA EOS, Aspen Plus can
represent the system with observed accuracy. The following two pages
include sample experimental data vs. regressed CPA.

Contents2 Physical Properties 7

 Figure 2A: T-xy diagram comparing experimental data and regressed Cubic
Plus Association equation of state for the binary interaction between ethylene
oxide (EO) and water

Figure 2B: P-xy diagram comparing experimental data and regressed Cubic
Plus Association equation of state for the binary interaction between ethylene
oxide (EO) and water

8 2 Physical Properties
 Figure 2C: P-xy diagram comparing experimental data and regressed Cubic
Plus Association equation of state for diethylene glycol (DEG) and water
(H2O)

Figure 2D: T-xy diagram comparing experimental data and regressed Cubic
Plus Association equation of state for tetraethylene glycol (4EG) and water

Contents2 Physical Properties 9

 Figure 2E: P-xy diagram comparing experimental data and regressed Cubic
Plus Association equation of state for tetraethylene glycol (4EG) and water

10 2 Physical Properties
3 Reactor Model

The reactor model was developed using reaction kinetics outlined by Melhem
et. al.1 The activation energy was derived from the studies around the
hydrolysis reaction between water and ethylene oxide1. The activity of
glycols heavier than monoethylene glycol were considered to have a reaction
rate twice as large, as suggested1. This derives an equilibrium constant that
is twice as large for DEG, TEG, and 4EG than for MEG. The overall activity
was tuned to match reaction completion estimates that the reaction comes to
>99% completion at ~30% of the reactor length. See Figure 3A for a
composition diagram.

Figure 3A: Composition diagram from Aspen Plus for the reaction system with
the model inputs (excluding water)
The reactor considered is a 193 foot long pipe reactor based on specifications
reported by Interrnational Process Plants3. The assumptions are a
noncatalytic reaction in an adiabatic vessel with homogeneous plug flow.
These assumptions translate well into using the RPlug reactor block (plug flow
reactor). In Figure 3B, find comparisons between the Aspen Plus RPlug model
used, literature predictions with rigorous kinetics, and experimental test data.

Contents3 Reactor Model 11

Figure 3B: Comparison of measured data, literature predictions, and Aspen predictions
(RPlug reactor model with kinetics) for 5 different data sets evaluated from Melhem et. al.1

12 3 Reactor Model
4 Evaporator

Triple effect evaporators are often used to remove water from glycols. In a
true triple-effect evaporator, the heat from steam would be used to evaporate
water off of the glycol solution. The generated steam would be used to
provide heat to the next evaporator, and so forth.
In this example, bulk steam is split into three streams using an FSPLIT block.
The heat from each stream is supplied to a FLASH2 block, each acting as a
chamber for evaporation. The steam will condense as heat is supplied to
each evaporator chamber. The three evaporation chambers remove >90% of
the water from the glycol reactor product stream.

Figure 4A: Diagram of the triple-effect evaporator modeled in Aspen Plus

Contents4 Evaporator 13
14 4 Evaporator
5 Separation Train

The downstream separation train includes 4 distillation columns in series; 1

dehydration column and 3 columns recovering high-purity, polyester grade3,
MEG. All columns are modeled using RADFRAC blocks with internal design
specifications. Figure 5A shows a diagram of the separation section in Aspen
Plus, drawing high-purity products for MEG, DEG, and TEG.

Figure 5A: Diagram of the glycol separation train modeled in Aspen Plus
The first distillation column is a dehydration column, removing >99.9 wt% of
the remaining water in the system, totaling >99.99 wt% water removal from
glycol in the overall process. The design specs on the column achieve
99.96% mole recovery of water from the overhead stream, while
manipulating the reboiler duty. Solving with the defaults, the 9 stage column
operates with a ~25 MW reboiler heat duty and a reflux ratio of 0.32.
The hydraulic pressure drop in the column was simulated by exporting results
from the new Column Analysis feature in V9 Aspen Plus. This feature takes
the number of stages as actual stages to design internals within a feasible
operating envelope. Some of the boundaries considered include jet flood,
downcomer backup, weeping, min/max weir loading, etc. Using the feature,
structured packing was selected based on the vapor/liquid traffic in the
column, since Koch-Glitsch Flexipac “X” packing can typically handle higher
capacities with lower pressure drops. There are two packing sections in the
column with diameter of 4.75 meters. The “update pressure drop from top
stage” option was selected to refresh the simulation with the hydraulic

Contents5 Separation Train 15

 pressure drop calculation, which effects separation. Please note, all column
internals in this example are representative and not based on actual column
implementations. See the internals specification form in Figure 5B.

Figure 5B: Internals form for the dehydration column. Detailed column
internals are defined for trays or packing
The hydraulic calculations in Column Analysis plot the operating point for
packing with respect to multiple isobars to identify pressure drop, shown
below. Shown in Figure 5C, the current internals selection translates to a
stable operating region for the column.

Figure 5C: Hydraulic plot results for Flexipac internals in the specified
dehydration column
MEG is the primary product in this system, being recovered at a rate of ~67
tonne/hr with >99.9 wt% purity. The column has 26 stages with design
specifications for 99.99 mole recovery of MEG at 99.95 wt% purity, by

16 5 Separation Train
 varying the reboiler duty and reflux ratio. With the base case, the reboiler
duty is ~23 MW and reflux ratio is ~0.32.
The hydraulic pressure drop was generated with a feed location at stage 16.
The top section (stages above the feed) includes structured Flexipac “X”
packing with a diameter of 5.5 meters. The bottom section has a higher
vapor/liquid holdup, so sieve trays with a diameter of 7 meters is used (the
diameter is calculated in Column Analysis to satisfy jet flood constraints). The
internals are specified in input forms with diagrams representing the actual
geometry of the tray, shown in Figure 5D.

Figure 5D: Tray internals for the bottom section of the MEG column
The internals, including downcomer geometry, result in a column within a
feasible operating envelope, shown in Figure 5E.

Contents5 Separation Train 17

 Figure 5E: Hydraulic plot results for sieve tray internals in the MEG column
DEG is recovered at ~ 8.4 tonne/hr with 99.9 wt% purity. The column has 16
stages, with design specifications for 99.9 wt% mass purity of DEG and
99.99% mole recovery, while varying the reflux ratio and reboiler duty. With
the base case results, the reboiler duty is ~2.2 MW and the reflux ratio is
~0.7. Two Flexipac “X” structured packing sections are considered for the
column internals, above and below feed stage 9 for the column of 3.5 meters.
The hydraulic pressure drop is
TEG is recovered at ~0.5 tonne/hr with >99 wt% purity. Heavier glycols
(4EG) are recovered in the bottoms product stream of the final column.
Further separation may be required to simulate the recovery of high-purity
4EG. The 12-stage column includes a design specification for 95% mole
recovery of TEG, while varying the reboiler ratio (equal to 0.1 in the base
case). Column Analysis is omitted from the final column.

18 5 Separation Train
6 Overview & Model
Applications

The model simulates a simplified end-to-end production of ethylene glycol

from ethylene oxide and water. Glycol products are recovered at high purity
and high recovery, as shown with the stream summary table in Figure 6A.

Figure 6A: Mass flows and mass fractions for entire process from the reaction (R-IN to R-
OUT) through the evaporation step (CONC3) and through separating out relatively pure
glycol streams.
The flowsheet has a custom table for the ethylene oxide mass flow input to
the system. The default value is 55 tonne/hr. This can be increased up to 65
tonne/hr to identify the tradeoff between increased production and increased
energy consumption. Beyond this range, the hydraulic constraints for the
column may be violated and column convergence difficulties may arise. The
amount of water into the system is kept constant at 55 tonne/hr.
Restart and run the simulation for each change in input. The simulation may
take a minute or two to run. The column duties and product mass flow rates
are displayed on the Aspen Plus flowsheet.
Further, the downstream distillation columns can be updated to reflect the
grade of ethylene glycol produced. This example shows the production of
polyester grade monoethylene glycol, at >99.9 wt% purity. For industrial
grade MEG, purity needs to be >99.1 wt%, and for antifreeze grade MEG,
purity needs to be >95 wt%4.
With a change in desired purity, design changes can be made to
accommodate (decrease number of column stages, decrease reboiler duty,
etc.).The entire process model can also be scaled to meet production criteria
in your plant.

Contents6 Overview & Model Applications 19

20 6 Overview & Model Applications
7 Citations

1 “Kinetics of the reactions of ethylene oxide with water and ethylene

glycols”, Georges A. Melhem, Arturo Gianetto, Marc E. Levin, Harold
G. Fisher, Simon Chippett, Surendra K. Singh, Peter I. Chipman; Process
Safety Progress, 2001, 20 (4), 231-246
2 Rebsdat, Siegfried and Mayer, Dieter (2005) "Ethylene Oxide" in Ullmann's
Encyclopedia of Industrial Chemistry. Wiley-VCH, Weinheim
3 Joachim, Michael and Rege, Sanjeev, “World Scale Ethylene Glycol Plant”
International Process Plants,
<http://www.ippe.com/plants/600593/EG_PPT.pdf>
4 MEGlobal, “MEG Sales Specifications” EQUATE Petrochemical Copmany,
July 2004. < http://www.meglobal.biz/monoethylene-glycol/sales-specs>

Contents7 Citations 21