Design Guidelines for Distillation Columns

in Ethyl-benzene and Styrene Monomer Service

Peter W. Faessler
Karl Kolmetz
Wai Kiong Ng
Krishnamoorthy Senthil
Tau Yee Lim

Sulzer Chemtech Pte. Ltd.

Singapore

Andrew W. Sloley

Veco USA, Inc

Bellingham, Washington

Timothy M. Zygula

Nova Chemicals Corp.

Pasadena, Texas

Prepared for,

DISTILLATION 2005
2005 Spring AIChE Meeting
Atlanta, Georgia
April 10-14, 2005

Abstract

Styrene monomer is the fourth largest chemical produced on an industrial scale and most ethyl-
benzene is utilized in styrene monomer production. The largest chemical produced on an industrial
scale is ammonia for fertilizer production, followed by crude oil refining, and then ethylene by furnace
pyrolysis. Styrene monomer has been manufactured commercially for more than fifty years with
advances in the key unit operation areas of reactor design and distillation.

The original distillation internals were trays, which have faced many challenges in services that are
prone to polymerization. The higher pressure drop and longer residence time of trays are
disadvantages in this service. First generation structured packing was introduced in 1980’s. This
advance greatly improved styrene distillation operations. The limit of first generation structured
packing was capacity, where the stage efficiency began to decrease.

The rapid progress in computational fluid dynamic modeling (CFD) over the last ten years has also
led to further improvements in the optimization of column internal design. CFD modeling of the
structured packing, vapor-liquid distributors, and feed inlets can improve the performance of a
distillation column.

Contemporary styrene unit designs include second generation structured packing and optimized
liquid-vapor distributors. In the current designs, consideration of packing bed height and how the
packing bed height affect stage efficiency due to mal-distribution should be reviewed. Designs are
now limited by the maximum allowable pressure drop in order to avoid bottoms temperatures above
120°C (248°F) to 122°C (252°F). The authors will review the progression of Styrene Monomer
Distillation advances and where the future research might be exploring.
Introduction

The ethyl benzene and styrene monomer industry is a mature industry with basically two technology
licensers; 1) ABB Lummus and 2) Shaw Stone & Webster Badger. The technology has the typical
two unit operations, reaction followed by separation. Each operation can be optimized and there is on
going research in each area to improve the conversion of the reactors and the efficiency of the
separation.

The advances in reactor technology in ethyl benzene conversion include converting from gas phase
to liquid phase reactors utilizing zeolite catalyst with a greater the 95% yield. The advances in reactor
technology in the styrene monomer conversion include continuous addition of active catalytic
components and advances in the endothermic reheat technology, which utilizes deep vacuum,
adiabatic dehydrogenation.

The original distillation internals were trays, which have faced many challenges in services that are
prone to polymerization. The higher pressure drop and longer residence time of trays are
disadvantages in this service. First generation structured packing was introduced in 1980’s. This
advance greatly improved styrene distillation operations. The limit of first generation structured
packing was capacity, where the stage efficiency began to decrease.

Ethyl Benzene Overview

Reactor Overview

In the early 1970's, aluminum chloride technology was the preferred means for the production of
ethylbenzene (EB). However, environmental concerns and the high maintenance costs associated
with this technology created a market for alternative processes. In response, technology licensers
developed new processes.

The process consists of two major subsystems:

1. An alkylation section, where ethylene is reacted with benzene

2. A distillation section, where un-reacted benzene, PEBs (Poly Ethyl Benzene), and heavier
compounds are separated from the alkylation and secondary reactor effluents to produce
EB of high purity.

In the alkylation section, ethylene is reacted with benzene in a liquid-filled reactor that is equipped
with multiple fixed-catalyst beds. A portion of the total ethylene feed is injected upstream of each bed.
The benzene feed is heated to reaction temperature prior to being introduced to the first reactor bed.
The heat of reaction is used to generate steam. (3)

Distillation Overview

The distillation section consists of three or four columns, each of which can generate steam in its
overhead system. The benzene column separates untreated benzene from the reactor effluent.
Distillate from the benzene column is recycled to the reactor system, and its bottoms feed the second
distillation column, where the EB product is recovered as liquid distillate. The bottoms from the
second column feed the PEB column, which recovers recyclable PEBs for conversion to EB in the
transalkylation reactor. Bottoms from the PEB column, which consist primarily of diphenyl compounds,
are withdrawn from the process as a residue stream. (3)
 ALKYLATION BENZENE RECOVERY EB RECOVERY

INHIBITOR BE INHIBITOR EB PEB

ETHYLENE LIGHTS

ETHYLENE STEAM

ETHYLENE

BENZENE

FLUX OIL
PEB
ETHYLENE
BE

Advances in Ethyl Benzene

In recent years, interest has been growing in using dilute ethylene from fluidized catalytic cracking
(FCC) off-gas to produce ethylbenzene (EB). Although efforts for economically converting the off-gas
ethylene into a more valuable petrochemical product (instead of using it as a fuel in refinery
operations) were initiated in 1950s, it was not until May 1991 that the first commercial EB unit using
dilute ethylene as feedstock came on stream at Shell' s Stanlow, United Kingdom plant. The plant,
based on the vapor-phase benzene alkylation technology of Mobil/Badger was soon followed by
Dow' s unit at Ternuezen, the Netherlands. The Dow plant, built in late 1991, is also based on
Mobil/Badger technology.

Recently, Dow has patented a different approach for EB production. In its new process version,
ethylene is generated by the catalytic dehydrogenation of ethane instead of using cat-cracker off-gas
as its source or polymer-grade ethylene as the feedstock. Gallium- or zinc-promoted mordenite
catalyzes ethane dehydrogenation to ethylene at a milder temperature of 700°C (1292°F) that the
higher temperature range of 800-875°C (1472-1607°F) employed in steam cracking of ethane.
Conversion of ethane is about 14 to 50 wt%, depending on the promoter used, and selectivity to
ethylene is 85 wt%. Dow states that the products from the dehydrogenation reactor are free of
acetylene and butadiene, and can be directly fed into the alkylation reactor for EB production without
purification of the dilute ethylene stream. The benzene alkylation reaction is catalyzed by
dealuminated mordenite, and the reaction products are separated by conventional means such as
distillation to obtain EB. Unreacted ethane and benzene are recycled. Lower per-pass conversion
rates in the alkylation phase depress formation of aromatic by-products, whose presence adversely
affects product purity.

The Dow process is probably appropriate only for a region where ethane is abundantly available, and
where FCC off-gas or ethylene are not. Alternatively, the Dow process may be a useful, innovative
technology for the large-scale catalytic production of ethylene because its process economics are
comparable to those of conventional ethane cracking units. (6)
Ethyl Benzene Distillation Guidelines

The EB distillation section consists of three or four columns, each of which can generate steam in its
overhead system.

Benzene Recycle Column

The first column is typically the benzene recycle column. This column removes the un-reacted
benzene and the reacted products are in the tower bottoms. In this column the overhead condenser
can be utilized to generate steam. This requires the column to be at medium pressures, therefore
trays are typically specified. Typically about 60 trays are utilized. This is a straight forward distillation
column.

Benzene Drying Column

The second column is the benzene drying column and the overhead condenser can be utilized to
generate steam. This requires the column to be at medium pressures, therefore trays are typically
specified. Typically about 50 trays are utilized. This is also a straight forward distillation column.

EB Recovery Column

The third column is the EB Recovery Column. This column is designed at lower pressures (1.7 bar)
to reduce the polymerization of the heavy reacted products. Earlier designs utilized trays in this
application. Present designs utilize structured packing and trays to increase capacity.

EB Recovery Column Guidelines

Separation columns where relative volatility between the key components is higher than 2.0 and more
than 40 theoretical stagers are required; column design has to consider at least two packed beds with
a single bed height not exceeding 15 theoretical stages and trays where applicable.

Looking into the styrene process we find similar conditions in the BE/TO separation column, EB
recovery column and in the EB plant, where PEB has to be separated from the heavies. These
columns are operating in the positive pressure range, as well as vacuum and have relative volatilities
higher than 2.0.

PEB Recovery Column

The final column EB distillation section is the PEB Recovery Column. Many designs for this column
are trays due to the high incidents of fouling. For revamp cases packing can be utilized with success,
but care needs to be taken in the design to cater for the high polymerization potential and feed inlet
devices.
Styrene Monomer Overview

Styrene monomer (SM) is an

important petrochemical used in the
production of polystyrene and other
styrenic resins such as acrylonitrile
butadiene styrene (ABS) and styrene
acrylonitrile (SAN). Ethylbenzene
(EB) is produced primarily by
alkylation of benzene with ethylene.
EB is then converted to SM by
dehydrogenation. (4)

Reactor Overview

The feedstock, ethylbenzene, is

catalytically dehydrogenated to
styrene in the presence of steam in a
fixed bed, radial flow reactor system.
The dehydrogenation reaction is
favored by low pressures and is
generally conducted under deep
vacuum. Toluene, benzene, and
some light compounds are formed as by-products. The overall reaction is endothermic with heat
supplied by steam in the adiabatic reactors. Reactor effluent waste heat is recovered through heat
exchange with combined feed and by generating steam which is utilized in the process. The off gas
stream is compressed, processed through the off gas recovery section, and used as fuel in the steam
super heater. The condensates from the condenser and off gas recovery section flow into the
separator where hydrocarbon and water phases separate. The dehydrogenated mixture is
fractionated to recover the styrene monomer product and recycle ethylbenzene, as well as benzene
and toluene by-products. Inhibitors are added to prevent styrene polymerization in the process
equipment. (4)
 Styrene Monomer Production

The energy needed for the reaction is supplied by superheated steam (at about 720 0C) that is
injected into a vertically mounted fixed bed catalytic reactor with vaporized ethylbenzene. The
catalyst is iron oxide based and contains Cr2O3 and a potassium compound (KOH or K2CO3) which
act as reaction promoters. Typically, 2.5-3 kg steam is required for each kilogram of ethylbenzene to
ensure sufficiently high temperatures throughout the reactor. The superheated steam supplies the
0
necessary reaction temperature of 550-620 C throughout the reactor. Ethylbenzene conversion is
typically 60-65%. Styrene selectivity is greater than 90%. The three significant byproducts are
toluene, benzene, and hydrogen.
Styrene Distillation Overview
After the reaction, the products are cooled rapidly (perhaps even quenched) to prevent
polymerization. The product stream (containing styrene, toluene, benzene, and un-reacted
ethylbenzene) is fractionally condensed after the hydrogen is flashed from the stream. The hydrogen
from the reaction is used as fuel to heat the steam (boiler fuel). After adding a polymerization inhibitor
(usually a phenol), the styrene is vacuum distilled in a series of four or five columns (often times
packed columns) to reach the required 99.8% purity. The separation is difficult due to the similar
boiling points of styrene and ethylbenzene. Typical capacity per plant ranges from 70,000 to 100,000
metric tones per year in each reactor and most plants contain multiple reactors or units. (5)

Badger Process

BENZENE

EB BENZENE/TOLUENE
COLUMN

EB
STEAM BENZENE/ TOLUENE
TOLUENE
RECYCLE EB/SM COLUMN
DEHYDROGENATION
COLUMN

SM STYRENE

SM
FINISHING COLUMNS
STORAGE TANKS

STRUCTURED PACKINGS
TRAYS TAR CONCENTRATOR

TAR RESIDUE
Styrene Distillation Guidelines

There are typically five columns in the Styrene Distillation Process, which can be ordered different by
each licenser.

Benzene Toluene Recycle Column

This can be the first column after the reaction section. The purpose of this column is to remove the
light reactant products, which are benzene and toluene, from the Styrene Product. This column can
be trays, packing or a combination of the two.
Case Example of a revamped Benzene Toluene Recycle Column
Typical mass balance for this column
Feed Distillate Bottom
BENZENE (BE) 1.10 34.79 --
TOLUENE (TO) 2.70 65.00 0.65
ETHYLBENZENE (EB) 33.30 0.19 34.43
AROMATICS 0.70 0.01 0.71
STYRENE (SM) 62.10 0.01 64.10
HEAVIES 0.10 -- 0.11

External reflux ratio : 13.0

Top pressure : 225 mbar
Top temperature : 58 °C
Bottom pressure : 425 mbar
Bottom temperature : 112°C
Number of trays on top : 20 to 25
on bottom : 10 to 15
total : 30 to 40

Original Design – 40 trays were replaced with three bed of structured packing

T.L. expected NTS

8.4 m 250.Y/X 18

ID 1700
feed
22 m
40 trays 2.5 m 250.X 5

6.1 m 250.X 12
Results of the 1st revamp

Feed Distillate Bottom

expected measured expected measured

BE 1.10 34.80 35.43 - 0.02

TO 2.70 65.00 61.75 0.65 0.82
EB 33.30 0.19 2.65 34.40 34.30
Arom. 0.70 0.01 0.02 0.71 0.71
SM 62.10 0.01 0.20 64.10 64.05
Heavies 0.10 - - 0.11 0.10

External reflux ratio expected : 13.0

External reflux ratio measured : 16.40

Data was gathered and then simulated.

Simulating the measured results the following bed efficiencies emerged:

expected guaranteed measured

above feed 18 TS 14 TS 9 - 7 TS

below feed 12 + 5 TS 14 TS 3 - 5 TS

Total 35 TS 28 TS 12 TS

The result of the simulation and process study determined that there were insufficient stages in the
rectifying section. The feed point was lowered to increase the rectifying section fractionation ability.
Feed Point before - Stage 15

Feed point

stripping section

Feed point after - Stage 13

Feed point

stripping section
Operation results with feed in new location

Feed Distillate Bottom

guaranteed measured guaranteed measured
BE 0.92 24.31 0.08
TO 2.85 73.87 0.65 0.29
EB 32.25 0.19 0.07 33.42
Arom. 0.57 1.75 0.52
SM 63.35 -- 65.61
Heavies 0.08 -- 0.08

External reflux ratio expected : 13.00

External reflux ratio measured : 13.10

Simulation with new feed location showed following efficiencies:

expected guaranteed measured

above feed 18 + 5 TS
18 TS 17 + 5 = 22 TS
below feed 12 TS
10 TS 14 TS
Total 35 TS
28 TS 36 TS
EB / SM Splitter Column
The purpose of an ethyl benzene (EB) / styrene
splitter is to separate ethyl benzene from styrene.
The distillate EB is recycled to Styrene reactors and
the bottom product Styrene Monomer (SM) is sent to
the Styrene Finishing column for heavy key removal.
The EB impurity in the SM should be in the range of
100 ~ 500 ppm.
EB/SM Splitters are operated under vacuum due to
the polymerization potential of styrene at elevated
temperature. Polymers are undesirable in the
monomer distillation column and can lead to plugging
of distributors or packing and unit outages.
The rate of polymerization is directly proportional to
time and increases exponentially with temperature.
Both residences time and temperate must be
minimized to reduce polymerization deposits. Current
guideline is to keep the tower bottoms temperature
below 120°C
Generally steam ejector systems are used to
maintain vacuum at the top of the tower. The typical
column top pressure is 100 to 400 mbar and the
internals are carefully designed to reduce the tower
overall pressure drop, minimize liquid hold up; reduce the bottom temperature and residence time.
Some producers are increasing the tower pressure due to improvements in inhibitor formulations.
This can increase capacity and improve heat recovery.

Ethyl Benzene/Styrene Splitter Service Design Guidelines

During the early days of styrene manufacturing, trays were used as column internals for the
separation. The trayed columns have a high-pressure drop and high bottoms temperature. Currently
the industry standard is to use high-capacity structured packing as column internals for EB/SM
splitters.
The EB/SM splitter may require 80 to 100 theoretical stages depending on the purity requirements.
The columns may have 5 to 7 beds of structured packing and require very good quality liquid
distributors and collectors.
 Table of Number of Theoretical Stages Verses Reflux Ratio
at Different Pressures

NTS versus Reflux-Ratio

120

100

80
NTS

60

40

20

0
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30
Reflux Ratio

P=150mbar

NTS Versus Reflux-Ratio

120

100

80
NTS

60

40

20

0
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34

Reflux-Ratio
P=400mbar

CASE NTS Condenser

Top Pressure (mbar) Reboiler (M.W) (M.W) Reflux-Ratio

1 150 71 38.43 39.47 8.1726

2 400 79 42.45 42.94 8.1726

A special design for overhead condenser and reboiler may be used to reduce the overall column
pressure drop. Some of the advantages of using structured packing in these applications are as
follows:

1. Minimum polymer formation because of reduced pressure drop leading to low tower bottoms
temperatures. The pressure drop for high capacity structured packing may be in the range of
1 - 4 mmHg per meter.
2. Low inhibitor consumption because of low bottom temperature and minimum liquid hold-up,
which results in significant savings in the costs of operation.
3. Smaller residence time distribution of the liquid phase is achieved with high capacity
structured packing as compared to tray columns. It also reduces dead pockets and thermal
degradation, which usually gives rise to further acceleration of polymer formation.
4. Increase in capacity, yield, and purity when compared to tray column of same size.
5. Energy saving by increasing the number of theoretical stages when the columns are
revamped from trays or conventional packing to high capacity structured packing.

Many trayed towers have been up graded to structured packing due to the polymer formation. Here is
an example of polymer formation in a trayed styrene tower.

Attached is a case example of one revamp.

 Case example of trays verses packing with 200% increase

Typical Mass Balance in wt% After Revamp with 200% increase

Feed Distillate Bottom

Before After Before After
Benzene ~0 ~0 ~0
Toluene ~0.01 0.028 0
Ethylbenzene 33.3 97.972 98.4718 100 ppm
Styrene 61.9 2.00 1.5 92.8010 92.82
Heavies 4.75 ~0 7.189 7.17
Design Case: 100% 200%

Before After

Reflux Ratio (External) : 21.2 8.8

Pressure Drop Across Tower: 225 mm Hg 45 mm Hg
Top Temperature: 140-150°F
Bottom Temperature: 235°F 185°F
Number of Stages top : 15 to 20 25 to 30
on bottom : 35 to 40 55 to 60
total : 50 to 60 80 to 90

st
The early design philosophy for EB/SM splitters relies mostly upon structured packing, notably 1
generation 250.Y. Most of the columns featuring trays have been converted to packed columns due to
process advantages generated by low pressure drop and liquid handling within the column and its
ancillaries.
st
The limit of 1 generation structured packing was the total pressure drop with increased the tower
bottoms temperature to the polymerization limit of 120 degrees C.
Case Example of 1st Generation Packing to 2nd Generation Packing with 140% increase
st
Converting 1 generation structure packing to 2ndgeneration structure packing can lead to capacity
increases of as much as 140%. Attached is a typical example.

Typical Mass Balance in wt% After Revamp with 140% increase

Feed Distillate Bottom

Benzene 0.02 0.0501 --

Toluene 1.0 2.6278 --
Ethylbenzene 34.9 91.97 <100 ppm
Xylenes 1.3 3.35 0.031
Styrene 60.16 2.00 95.72
Heavies 2.64 -- 4.25
Design Case: 100 % 140%

Before After

Reflux Ratio (External) : 9.2 7.8

Pressure Drop Across Tower: 85-90 mm Hg 115-120 mm Hg
Top Temperature: 110-115°F 112°F
Bottom Temperature: 200°F 210°F
Number of Stages top: 20 to 25 25 to 30
on bottom: 50 to 55 75 to 80
total: 70 to 80 100 to 110

nd
The new 2 generation high capacity packing offers even lower pressure drop and improved process
conditions. As such, the packing is suitable for replacement of both Mellapak and trays in existing
columns as well as for the applications in new columns. Two items are worth noting: first a much
lower pressure drop and consequently lower bottom temperature, second a substantial reduction in
product hold-up.
Both items mean an enormous reduction of risk of polymer formation. To reduce the fear of fouling
with polymer below the feed level we can supply our structured packings also with smooth surface, if
preferred. Assuming that every reduction of 10°C in the bottom halves polymer formation and hold-up
as well as mean residence time are proportional for polymer formation, the solution with structured
packings compared to trays means lowering risk of polymer formation by a factor of more than 8.
Furthermore anti polymer chemical consumption is also half because of half the tower inventory.
nd
The limit of 2 generation structured packing is the total number of stages per bed to reduce mal
distribution. Mal distribution studies have limited current designs to 15 theoretical stages per bed.
Current research is investigating how to increase the bed heights and reduce the number of
redistributors, reducing total column height.
Typical EB/Styrene Splitter Conditions

EB/SM Splitter
Column configuration
Column Design
Number of beds: 5–7
Diameter for world scale plant* : 8–9m
Standard internals before 1980: Trays
Standard internals 1980 - 2000: Mellapak 250Y
Standard internals since 2000: MellapakPlus 252Y / 452Y

Operational parameters
Column top pressure 100 – 400 mbar
Energy / product (MW / t SM)** 0.6 - 0.8
Distillate specification 1 - 2% SM
Bottoms specification 50 – 500 ppm EB
Styrene Finishing Column

The last column can be one or two column depending on the technology licenser. The columns can
be trays, packing or a combination of both. Care needs to be taken in the design of this column due
to the high polymerization potential of this column.

SM Finishing Column
Column configuration
Number of beds: 2
Design Diameter for world scale plant* : 4–5m
Standard internals before 1980: Trays
Standard internals 1980 - 2000: Trays / Mellapak
Standard internals since 2000: MellapakPlus 252Y

Operational
parameters
Column top pressure 100 – 150 mbar
Energy / product (MW / t SM)** 0.15 - 0.20
Distillate specification 99.80 - 99.95 wt% SM
Bottoms specification 30 - 70 wt% SM

Conclusions

Contemporary styrene unit designs include second generation structured packing and optimized
liquid-vapor distributors. In the current designs, consideration of packing bed height and how the
packing bed height affect stage efficiency due to mal-distribution should be reviewed. Designs are
now limited by the maximum allowable pressure drop in order to avoid bottoms temperatures above
120°C (248°F) to 122°C (252°F).

Present ethyl benzene and styrene monomer reactor and distillation system are being improved with
time. Current research is on going to improve each section. Present limits for the distillation section
are the bed heights due to mal distribution. Investigations are to improve distributor and packings to
increase this limit.
References

1. Karl Kolmetz, Dr. Wai Kiong Ng, Siang Hua Lee, Tau Yee Lim, Daniel R. Summers, Cyron
Anthony Soyza, Optimize Distillation Column Design for Improved Reliability in Operation and
Maintenance, 2nd Best Practices in Process Plant Management, Nikko Hotel, Kuala Lumpur,
Malaysia, March 14-15, 2005

2. Mauro Damiani, Advantages of the New Generation of Structured Packing for EB/SM
Recovery Column Applications, Sulzer Chemtech Ltd., Winterthur, Switzerland

3 Exxon Mobil website,

http://www.exxonmobilchemical.com/Public_Products/TechLicensing/Worldwide/Technologies
/Tech_Technologies_Aro_EBMax.asp

4. UOP website, http://www.uop.com/aromatics/3020.html

5. Cheresources website, http://www.cheresources.com/polystymonzz.shtml

6. PEP website, http://www.process-economics.com/survey/wwwroot/PEP1/Reviews/97-3.htm

7. Christina J. Campbell, Industrial Experiences of MellapakPlus® in the Styrene Distillation

Field, Sulzer Chemtech USA, Inc. Tulsa, Oklahoma

8. Karl Kolmetz, Andrew W. Sloley, Timothy M. Zygula, Peter W. Faessler, Dr. Wai Kiong Ng, K.
Senthil, Tau Yee Lim, Designing Distillation Columns for Vacuum Service, The 11th India Oil
and Gas Symposium and International Exhibition, 6-7 September 2004, Grand Hyatt,
Mumbai, India