Chemical Process Industry

Module 13: Aromatics Units

CPI Technical Manual

2012, NALCO
DECEMBER 4, 2012
 Aromatics Units

Table of Contents

Overview ....................................................................................................................................................... 3
Equipment in an Aromatics Unit .................................................................................................................... 3
Definitions...................................................................................................................................................... 3
Diene Number ............................................................................................................................................... 4
Styrene Conversion ....................................................................................................................................... 4
Bromine Number ........................................................................................................................................... 4
Problems in a 1st Stage Hydrotreater ........................................................................................................... 4
Depentanizer Neutralizer Program ............................................................................................................... 5

CPI Technical Manual 13-2 of 5

- Nalco Confidential -

Overview
Many ethylene plants have an associated
aromatics unit. This unit consists of a 1st stage
hydrotreater and associated equipment,
depentanizer, deoctanizer, rerun tower, and a 2nd
stage reactor. Some 2nd stage reactors are
desulfurizers and hydrodealkylators that produce
benzene, and some 2nd stages simply desulfurize
and produce BTX (benzene, toluene, and xylene).
There are often other, more specific towers such
as a benzene tower in the aromatics unit, but the
variations are too numerous to mention.
Generally, the debutanizer bottoms combines with
the gasoline stripper bottoms to make up the feed
to the 1st stage hydrotreater. The gasoline stripper
takes feed from the compressor knockout pots.
Dripolene streams purchased outside can also be
added to contribute to the 1st stage feed. The 1st
stage effluent feeds the depentanizer and the
bottoms go to the deoctanizer. The deoctanizer
overhead goes to the 2nd stage reactor, and the
deoctanizer bottoms feed the rerun tower. The
rerun tower overhead is primarily a C 9 /C 10 stream.
Some of this stream is wash oil for the
compressors and the rest is sold as a hydrotreated
pyrolysis gasoline.
Equipment in an Aromatics Unit
1st stage hydrotreater: A palladium-based
catalyst is used in the presence of hydrogen to
reduce reactive double bonds to single bonds.
An example is the conversion of styrene to
ethylbenzene. The hydrotreater consists of a
guard bed and usually two packed beds.
Hydrogen gas is introduced into the feed
upstream of the guard bed.
Hot and cold separators: The hot reactor
effluent is condensed in a cold separator and
the light components are removed. The cooled
overhead effluent goes through a hot
separator to further remove lights. The
bottoms product from both exchangers feeds
the depentanizer.
Depentanizer: C 5 s are removed from the
CPI Technical Manual
- Nalco Confidential -
Aromatics Units
depentanizer as a side draw, near the top of
the tower. Corrosion in the overhead due to
acetic acid is often a problem in depentanizer
service.
Deoctanizer: Removes C 6 C 8 out the top and
C 9 + leaves as the bottom stream.
2nd stage hydrotreater: The deoctanizer
overhead stream feeds the 2nd stage
hydrotreater, which uses a metal catalyst and
hydrogen to reduce double bonds further,
remove sulfur and, in some cases, cleave the
alkyl group from Toluene and Xylene.
Rerun Tower: The rerun tower removes C 9
and sometimes C 10 as an overhead stream.
This stream can be used as wash oil in the
compressors and sold as a hydrotreated
pyrolysis gasoline stream. The bottoms are
usually sent back upstream to the primary
fractionator to be used as fuel oil. Occasionally
it is used as wash oil instead of the C 9 stream.
Definitions
The potential gum test involves taking 100 ml of
test sample and heating it in a Parr bomb at a
specified high temperature under an oxygen
atmosphere. Any reactive molecules in the pygas
are forced to polymerize. After a specified
amount of time, the sample is removed from the
bomb and stripped of the remaining liquid. The
non-volatiles that remain are weighed and a
potential gum in mg/100 ml is obtained. A potential
gum does not exist in the stream; it is made in the
test. If there are any existent gums, which are
discussed below, they will also show up in the
calculating of the potential gums. The existent
gum has to be subtracted out. If the sample is
heated under nitrogen, the gums produced will be
significantly reduced. This shows the effect of
oxygen on forcing polymerization. Further testing
can be done with inhibitors to show their effect on
stopping polymerization.
As mentioned above, any existent gums (gums
that exist in the stream before testing) in the
stream and any heavies are also counted as
potential gums. Often this residue is washed with
13-3 of 5

hexane or heptane to remove the heavies, so that
a more accurate potential gum can be determined.
These gums would be called washed gums. The
existent gum test is simply a non-volatile residue
determination. The liquid is removed via a stream
of nitrogen and sometimes some gentle heating to
remove all volatile material.
Samples collected for gums testing should not be
collected in metal cans or left in a hot
environment. The metal can help catalyst
polymerization in the test and the hot environment
will increase the existent gums in the stream,
giving a falsely high number.
Generally, streams with less than 25 mg/100 ml of
existent gums are considered good for a dripolene
stream and less than 10 or 20 mg/100 ml is
acceptable for a potential gum for a hydrotreated
stream. A potential gum is normally done on a
hydrotreated stream. When it is done on an
unhydrotreated stream, the potential gums are
very high, since the stream still has reactive
double bonds.
Diene Number
After a stream has been hydrotreated, the 1st
stage reactor effluent is tested to determine how
much of the reactive double bonds have been
converted. A known amount of maleic anhydride is
added to the stream and allowed to undergo a
Diels-Alder cycloaddition reaction with the reactive
double bonds. The unreacted maleic anhydride is
measured and how much has been consumed is
calculated and called a Diene number. The stream
is tested for Diene number before and after
hydrotreating and a percent conversion is
determined.
Styrene Conversion
An easier way to determine percent conversion is
to assume all of the reactive double bonds are
styrene, which is reasonable because MOST of
the reactive double bonds are from styrene. A GC
of the percent of styrene in the feed to the
hydrotreated and the effluent are run and a
percent conversion is determined. Percent
conversions should range in the mid to high 90s
CPI Technical Manual
- Nalco Confidential -
Aromatics Units
when the hydrotreater is running well.
Bromine Number
A 1st stage hydrotreater predominantly reacts with
reactive double bonds. Those are double bonds
that are activated in some way, usually by being
conjugated. There are a number of molecules in
the stream that have unreactive double bonds,
and these will be less receptive to the
hydrogenation. However, it is useful to determine
just how many double bonds are present
reactive and unreactive. This is done with
Bromine, which is known to add across all double
bonds at room temperature. The amount of
bromine consumed is converted to a bromine
number, which when used along with the diene
number provide a good idea of what kind of
reactivity the stream has.
Problems in a 1st Stage Hydrotreater
Sharp increases of P across the catalyst beds
indicate fouling, which may be due to too reactive
of a stream and require inhibitors, or it may be due
to existent gums. Generally, our inhibitors in the
1st stage feed (from upstream programs such as
light ends) do not contribute to the fouling and do
not poison the catalyst. It is not unusual for Nalco
to be blamed, however, if fouling increases.
Checking the existent gums in the feed is the first
step, and identifying the source of the high gums
would be next. Recycle streams are most often the
culprits.
Besides existent gums, a high concentration of
butadiene in the feed can contribute to excessive
fouling in the reactor bed. The debutanizer is the
most logical place for butadiene to exist. Often,
high butadiene concentration in the feed will be
accompanied by high Ts across the first bed or
spikes in T. If high butadiene concentration is the
problem, first see if changes to the debutanizer
operation can reduce the butadiene. If not,
inhibitors can be added. If the T across all the
beds does not look uniform, there may be
problems with channeling in the bed, causing
some hot spots and cool spots. This data is
normally available on the DCS.
13-4 of 5
 Aromatics Units

In Figure 1, note that the high existent gums seen tank being turned the wrong way.
in May 1994 were due to a valve from a slop oil
Figure 1: Existent Gums in the GHU Feed

200
180
160
140 EC3053A was added to the GHU Feed
mg/100 ml

from 11/94 to 5/95 as shown in red

120
100
80
60
40
20
0
05/01/1994
05/29/1994
06/26/1994
07/24/1994
08/21/1994
09/18/1994
10/16/1994
11/13/1994
12/11/1994
01/08/1995
02/05/1995
03/05/1995
04/02/1995
04/30/1995
05/28/1995
06/25/1995
07/23/1995
08/20/1995
09/17/1995
10/15/1995
11/12/1995
12/10/1995
01/07/1996
02/04/1996
03/03/1996
Date

Also note the low gums from November 1994 to acetaldehyde; it and other organic acids are
May 1995. EC3053A was added to the feed to produced in ethylene furnaces. Most of the acids
reduce fouling in the reactor. The problems were are removed in the compressor knockout pots.
due to old catalyst and our inhibitor was not able These knockout pots feed a gasoline stripper (or
to compensate for that; however, the existent similar tower) and thus a 1st stage hydrotreater
gums were also reduced as seen in the graph. sees a significant amount of acetic acid from the
That is because the existent gum test itself creates gasoline stripper bottoms feed to that unit. Any
a small amount of gums when heat is applied. acid that does not get reduced in the 1st stage
reactor enters the depentanizer via the
Sulfur can be a temporary or permanent catalyst depentanizer feed. Acetic acid can azeotrope with
poison depending on the type and amount. light hydrocarbons. Therefore, most of the acetic
Typically, sulfur is a temporary poison and will acid in the depentanizer goes overhead with the
cause styrene conversion to drop when there are C 5 stream. There is some entrained water in the
high sulfur spikes in the feed.
feed (100 150 ppm estimate). This water will
The 2nd stage reactors differ from one unit to also go overhead in a depentanizer. When the
another, and there are normally not a lot of water condenses in the overhead condenser, the
opportunities for Nalco treatment programs. acetic acid goes into the water and creates a very
Excess styrene is often the cause and, depending corrosive stream. The overhead lines, condenser,
on the design, an inhibitor might help. In units and reflux drum are all subject to corrosion. In
where the product is BTX, corrosion is sometimes addition, upstream in the hot and cold separator
seen in the BTX tower in the overhead. A filmer is where water is still present, a low pH environment
generally recommended and sometimes these exists. The corrosion occurs primarily on the
towers also see some foaming. bottom of lines and tubes in small, deeply grooved
rivulets. It is very difficult to detect with thickness
Depentanizer Neutralizer Program scans.
Acetic acid is formed via the over-oxidation of
**End of Lesson**

CPI Technical Manual 13-5 of 5

- Nalco Confidential -