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Petrochemical Feedstocks
For aromatics production for petrochemical use, the catalytic reformer can be
operated at higher severity levels than for motor gasoline production. Highly
naphthenic feedstocks also aid in high aromatics yields because the dehydration
of naphthenes is the most efficient reaction taking place and provides the highest
yield of aromatics. Table 15.1 illustrates the increase in aromatics yields as the
reformer operating severity is increased [the clear research octane number (RON)
is the measure of operating severity].
The C 6–C 8 aromatics (benzene, toluene, xylene, and ethylbenzene) are the
large volume aromatics used by the petrochemical industry with benzene having
the greatest demand. The product from the catalytic reformer contains all of these
aromatics and it is separated into its pure components by a combination of solvent
extraction, distillation, and crystallization. In addition, because of the much
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greater demand for benzene, the excess of the toluene and xylenes over market
needs can be converted to benzene by hydrodealkylation.
The Udex process, using polyglycols, was the first of the solvent extraction
processes to find widespread usage. Many of these units are still in operation in
U.S. refineries but, since 1963, most new units have been constructed using the
Sulfolane or Tetra processes (Fig. 15.1b). At a given selectivity, the solubility
Petrochemical Feedstocks 305
Aromatics Separation
Benzene and toluene can be recovered from the extract product stream of the
extraction unit by distillation. The boiling points of the C8 aromatics are so close
together (Table 15.2) that separation by distillation becomes more difficult and
a combination of distillation and crystallization or adsorption is used. The ethyl-
benzene is first separated from the mixed xylenes in a three-unit fractionation
tower with 120 trays per unit for a total of 360 trays. Each unit is about 200 feet
in height, and the units are connected so they operate as a single fractionation
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Chapter 15
Figure 15.1a Sulfolane aromatics extraction unit.
Petrochemical Feedstocks
Figure 15.1b Tetra aromatics extraction unit.
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Chapter 15
Figure 15.2 Sequence of aromatics recovery operations.
Petrochemical Feedstocks 309
F C F C
Benzene 176.2 80.1 42.0 5.5
Toluene 231.2 110.6 —139.0 —95.0
Ethylbenzene 277.1 136.2 —139.0 —95.0
p-Xylene 281.0 138.4 55.9 13.3
m-Xylene 282.4 139.1 —54.2 —47.9
o-Xylene 291.9 144.4 —13.3 —25.2
tower of 360 trays. High reflux ratios are needed to provide the desired separation
efficiency because the difference between the boiling points of ethylbenzene and
p-xylene is only about 3.9F (2C). This is a very energy-intensive operation
and, with today’s energy costs, it is usually less costly to make ethylbenzene by
alkylating benzene with ethylene.
A typical processing sequence for the separation of C8 aromatics is shown
in Figure 15.3. After removal of the ethylbenzene by super-fractionation, the o-
xylene along with the higher boiling C9+ aromatics is separated from the p- and
m-xylenes by fractionation. The boiling point of o-xylene is more than 9.6F
(5C) greater than that of its closest boiling isomer, m-xylene, and it can be
separated economically in a 160-plate distillation column. The overhead stream
from this column is a mixture of m- and p-xylenes and the bottoms stream con-
tains o-xylene and the C9+ aromatics. The bottoms stream is processed further
in a 50-tray rerun column to separate 99+% purity o-xylene from the C9+ aro-
matics.
The mixed m- and p-xylene overhead stream from the fractionator is sent
to either the Parex unit or the crystallization unit to separate the m- and p-xylenes.
The UOP Parex process uses adsorption of p-xylene on a molecular sieve adsor-
bent to separate the m- and p-xylenes. The adsorbent is selected such that p-
xylene molecules will be adsorbed and the m-xylene molecules will pass through
the adsorbent bed. Recoveries of 96% per pass of pure p-xylene can be achieved
[4] as compared with 60–65% recovery of p-xylenes by the freeze-crystallization
process.
The p-xylene usually is stripped from the adsorbent with p-diethylbenzene
or a mixture of diethylbenzene isomers. The UOP process uses a simulated
moving-adsorbant-bed design.
If fractional crystallization is used for separation, the mixed m- and p-
xylene overhead stream from the fractionator is fed to the crystallization unit to
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Chapter 15
Figure 15.3 Processing sequence to produce C8 aromatics.
Petrochemical Feedstocks 311
Benzene
The primary source of benzene is from the refinery catalytic reforming unit, but
substantial amounts of benzene are also produced by the hydrodealkylation of
toluene. The process flow for a hydrodealkylation unit (HDA) is also similar to
that of an isomerization unit. The feed can be toluene or a mixture of toluene
and xylenes. It is heated to 1175F (630C) at 600 psig (4140 kPa) and charged
to an open noncatalytic reactor (L/D > 20) where thermal dealkylation of toluene
and xylenes takes place during the residence time of 25–30 seconds. The hydro-
genation step in the dealkylation reaction is highly exothermic [22,000 Btu/lb-
mole (12,220 cal/g-mole) of H2 consumed], and temperature is controlled by
injection of quench hydrogen at several points along the reactor. The hydrode-
alkylation reaction results in the conversion of about 90% of the aromatics in
the feed and selectively favors about 95% of the conversion to benzene. A small
amount of polymer is also formed, primarily diphenyl. A small amount of hydro-
gen sulfide or carbon disulfide is added to the feed to prevent catastrophic corro-
sion of the furnace tubes, and a small amount of the polymer is recycled to mini-
mize polymer formation [8].
Naphtha Wax
Coil outlet temp., F (C) 1100–1650 (730–900) 1100–1200 (595–650)
Pres., psig (kPa) 45 (310) 15–30 (103–207)
Steam/HC, wt% 0.3–0.9 0.12–0.15
C3 conversion, wt% 60–80 8–10
Petrochemical Feedstocks
Figure 15.5 n-paraffin recovery by adsorption.
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Cycloparaffins
Cycloparaffins are usually prepared by the hydrogenation of the corresponding
aromatic compound. For example, cyclohexane is prepared by the hydrogenation
of benzene. There are a number of processes licensed for this purpose [8].
The hydrogenation of benzene is carried out over platinum or Raney nickel
supported on alumina or silica-alumina. The hydrogenation reaction is highly
exothermic with the release of about 1150 Btu/lb (640 kcal/kg) of benzene con-
verted to cyclohexane. Reactor temperature is controlled by recycling and in-
jecting a portion of the cyclohexane produced into the reactors [8].
Tetralin and decalin are prepared by the hydrogenation of naphthalene us-
ing the same hydrogenation catalysts as used for producing cyclohexane. Here,
benzothiophene is a common impurity in naphthalene and causes the rapid deacti-
vation of the nickel and platinum catalysts. It is necessary under these conditions
to use a cobalt–molybdenum catalyst which has been presulfided to activate it [8].
NOTES
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