US 20170050899A1

(19) United States

(12) Patent Application Publication (10) Pub. No.: US 2017/0050899 A1
Tinger et al. (43) Pub. Date: Feb. 23, 2017
(54) PROCESS AND APPARATUS FOR THE BOID 5/8 (2006.01)
PRODUCTION OF PARA-XYLENE BOI. I./24 (2006.01)
(52) U.S. Cl.
(71) Applicant: ExxonMobil Chemical Patents Inc., CPC ........... C07C 5/2767 (2013.01); C07C 5/2729
Baytown, TX (US) (2013.01); B01J 19/2445 (2013.01); B0ID
(72) Inventors: Robert G. Tinger, Friendswood, TX if123:42, it299;
(US); Dana L. Pilliod, League City, TX (2013.01)
(US); Michel Molinier, Houston, TX
(US) (57) ABSTRACT
The present invention is an improved process and aroparatus
(21) Appl. No.: 15/346,115 for Rising para-Xylene, RAF with E. to a
(22) Filed: Nov. 8, 2016 process that involves the methylation of toluene and/or
a V8 benzene to selectively produce para-Xylene, wherein streams
O O having differing amounts of ethvlbenzene are separatel
Related U.S. Application Data E. in the ..., of St. A first yS.
(62) Division of application No. 14/969,327, filed on Dec. feed comprising Xylenes and ethylbenzene is provided to a
15, 2015, now Pat. No. 9,517,980. first para-Xylene adsorption section, and a second hydrocar
(60) Provisional application No. 62/154,774, filed on Apr. bon feed comprising xylenes and less EB than the first
30, 2015. hydrocarbon feed is provided to a second para-Xylene
s adsorption section. Segregating the feeds with differing
Publication Classification ethylbenzene contents increases the overall efficiency of the
adsorption of para-Xylene by the adsorption units. Efficiency
(51) Int. Cl. and energy savings may be further improved by Subjecting
C07C 5/27 (2006.01) the lower-content ethylbenzene stream to liquid phase
BOID 3/4 (2006.01) isomerization.
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US 2017/0050899 A1 Feb. 23, 2017

PROCESS AND APPARATUS FOR THE 40-50% metaxylene (MX), 15-25% PX, 15-25% OX, and
PRODUCTION OF PARA-XYLENE 10-20% EB. Unless otherwise noted herein, percentages are
% weight.
CROSS-REFERENCE OF RELATED 0006. The overhead mixture 5 is then to the PX recovery
APPLICATIONS unit 15, which may employ crystallization technology,
0001. This application claims the benefit of Provisional adsorption technology, or membrane separation technology.
Application No. 62/154,774, filed Apr. 30, 2015. These technologies separate PX from its isomers and are
capable of producing high purity PX up to 99.9%, which is
FIELD OF THE INVENTION taken from unit 15 via conduit 17. In the case where unit 15
is an adsorptive separation unit, such as a ParexTM or
0002 This application relates to an improved process and EluxylTM unit, the extract 17, which comprises a desorbent,
apparatus for producing para-Xylene, particularly the recov such as paradiethylbenzene (PDEB), needs to be separated,
ery of para-Xylene from streams having differing amounts of such as by distillation, from the desired extract PX in
ethylbenzene. distillation column 19. This generates a high purity PX
stream 27, which may contain light impurities Such as
BACKGROUND OF THE INVENTION toluene, non-aromatics and water that are removed in a
0003 Ethylbenzene (EB), para-xylene (PX), ortho-xy downstream column (not shown) to further improve PX
lene (OX) and meta-xylene (MX) are often present together purity. The desorbent is returned to the PX recovery system
15 via conduit 21.
in Cs aromatic product streams from chemical plants and oil 0007. The raftinate 65, which comprises mainly MX, OX,
refineries. Although high purity EB is an important raw EB, and desorbent is sent to fractionation column 37,
material for the production of styrene, for a variety of generating stream 35, containing MX, OX, and EB, and
reasons all high purity EB feedstocks used in styrene pro bottoms 63. The desorbent in the bottoms product 63 is
duction are produced by alkylation of benzene with ethyl returned to 15. Note that as used herein the term “raflinate’
ene, rather than by recovery from a Cs aromatics stream. Of is used to mean the portion recovered from the PX recovery
the three xylene isomers, PX has the largest commercial unit 15, whether the technology used is adsorptive separa
market and is used primarily for manufacturing terephthalic
acid and terephthalate esters for use in the production of tion, crystallization, or membrane. The stream 35 is sent to
various polymers such as poly(ethylene terephthalate), poly isomerization unit 43 to isomerize the MX and OX and,
(propylene terephthalate), and poly(butene terephthalate). optionally, EB to an equilibrium mixture of the four isomers.
While OX and MX are useful as solvents and raw materials Isomerization unit 43 may be a vapor phase or liquid phase
for making products such as phthalic anhydride and isomerization unit or both. The product of the isomerization
isophthalic acid, market demand for OX and MX and their unit 43 is sent via conduit 51 to the C distillation tower 53,
downstream derivatives is much smaller than that for PX. which separates the product of isomerization into a bottom
0004 Given the higher demand for PX as compared with stream 59 comprising equilibrium Xylenes and the overhead
its other isomers, there is significant commercial interest in 47, comprising C7 aromatics, e.g., benzene and toluene.
maximizing PX production from any given source of Cs The bottoms product 59 of distillation tower 53 is then sent
aromatic materials. However, there are a number of major to Xylenes re-run column 3, either merging with feed 1 as
technical challenges to be overcome in achieving this goal of shown in the figure, or it may be introduced by a separate
maximizing PX yield. For example, the four Cs aromatic inlet (not shown).
compounds, particularly the three Xylene isomers, are usu 0008. However, the presence of EB in the Cs aromatic
ally present in concentrations dictated by the thermodynam streams may impact the efficiency of certain processes
ics of production of the Cs aromatic stream in a particular described above. In particular, when an adsorptive separa
plant or refinery. As a result, the PX production is limited, tion unit is used for PX recovery, while the adsorbent has a
at most, to the amount originally present in the Cs aromatic higher affinity for PX, it may also adsorb EB to a significant
stream unless additional processing steps are used to extent, thereby reducing the adsorbent's capacity to adsorb
increase the amount of PX and/or to improve the PX PX. Thus, to avoid EB competing for adsorption capacity
recovery efficiency. A variety of methods are known to and increase the efficiency of PX adsorption, it is desirable
increase the concentration of PX in a Cs aromatics stream. to reduce or minimize the amount of EB in the Cs aromatic
These methods normally involve cycling the stream between stream sent to the adsorptive separation unit. Additionally,
a separation step, in which at least part of the PX is liquid phase isomerization converts little or none of the EB
recovered to produce a PX-depleted stream, and a xylene in the PX-depleted stream, and as a result, the amount of EB
isomerization step, in which the PX content of the PX in the xylenes loop can build up to very high levels. Thus,
depleted stream is returned back towards equilibrium con to maximize the use of liquid phase isomerization, it is also
centration. desirable to control the amount of EB in the PX-depleted
0005. In a typical aromatics plant, liquid feed, as shown stream Subjected to liquid phase isomerization.
in FIG. 1, typically a Cs aromatic feedstream which has SUMMARY OF THE INVENTION
previously been processed by known methods to remove
C, species (particularly benzene and toluene), is fed by 0009. The present invention is an improved process for
conduit 1 to a xylenes re-run column 3. The xylenes re-run producing PX, particularly with respect to a process that
column (or more simply a fractionation column) vaporizes involves the methylation of toluene and/or benzene to selec
the feed and separates the Cs aromatics into an overhead tively produce PX, wherein streams having differing
mixture 5 of xylenes (OX, MX, and PX) and ethylbenzene amounts of EB are separately treated in the recovery of PX.
(EB), and a bottom product 61 comprising Co. aromatics. A first hydrocarbon feed comprising xylenes and EB is
The overhead mixture typically has a composition of about provided to a first PX adsorption section, where a first
US 2017/0050899 A1 Feb. 23, 2017

PX-rich stream and a first PX-depleted stream are recovered ments, a first Xylenes fractionation column is fluidly con
from the feed. A second hydrocarbon feed comprising nected downstream of the vapor phase isomerization unit
xylenes and less EB than the first hydrocarbon feed is and upstream of the first PX adsorption section, and a second
provided to a second PX adsorption section, where a second Xylenes fractionation column is fluidly connected down
PX-rich stream and a second PX-depleted stream are recov stream of the liquid phase isomerization unit and upstream
ered from the feed. Segregating the feeds with differing EB of the second PX adsorption section.
contents increases the overall efficiency of the adsorption of
PX by the adsorption units. The first and second PX adsorp BRIEF DESCRIPTION OF THE DRAWINGS
tion sections may be individual PX adsorption units or 0012 FIG. 1 is a flow diagram of a conventional para
individual towers of a single PX adsorption unit. In embodi xylene (PX) production and extraction process which
ments, prior to the PX adsorption sections, the first hydro employs liquid phase Xylene isomerization and vapor phase
carbon feed may be passed through a first Xylenes fraction Xylene isomerization.
ation tower to produce a first overhead stream comprising Cs 0013 FIG. 2 is a flow diagram of one embodiment of the
hydrocarbons, which is sent to the first PX adsorption inventive process.
section, and a first bottoms stream containing Co. hydro
carbons. Similarly, the second hydrocarbon feed may be 0014 FIG. 3 is a flow diagram of a second embodiment
passed through a second Xylenes fractionation tower to of the inventive process.
produce a second overhead stream comprising Cs hydrocar 0015 FIG. 4 is a flow diagram of a third embodiment of
bons, which is sent to the second PX adsorption section, and the inventive process.
a second bottoms stream containing Co. hydrocarbons. 0016 FIG. 5 is a flow diagram of a fourth embodiment of
0010. The first and second PX-depleted streams, pro the inventive process.
vided to opposite sides of the dividing wall in a divided wall DETAILED DESCRIPTION OF THE
raftinate column, are then separated into an EB-rich stream INVENTION
and an EB-depleted stream. At least part of the EB-rich
stream is then fed to a xylene isomerization unit where the 0017. As used herein the term “C” hydrocarbon,
EB-rich stream is isomerized under at least partial vapor wherein n is a positive integer, means a hydrocarbon having
phase conditions to produce a first isomerized stream having n number of carbon atom(s) per molecule. For example, a Cs
a higher PX concentration than the first and second PX aromatic hydrocarbon means an aromatic hydrocarbon or
depleted streams. At least part of the EB-depleted stream is mixture of aromatic hydrocarbons having 8 number of
then fed to a xylene isomerization unit where the EB carbon atom(s) per molecule. The term “C+” hydrocarbon,
depleted Stream is isomerized under at least partial liquid wherein n is a positive integer, means a hydrocarbon having
phase conditions to produce a second isomerized stream at least n number of carbon atom(s) per molecule, whereas
having a higher PX concentration than the first and second the term “C-” hydrocarbon wherein n is a positive integer,
PX-depleted streams. Because vapor phase isomerization is means a hydrocarbon having no more than n number of
more effective at converting EB than liquid phase isomer carbon atom(s) per molecule.
ization, but liquid phase isomerization is more energy effi 0018. The present invention is an improved process and
cient, separating the PX-depleted streams based on EB apparatus for producing PX, particularly with respect to a
content and Subjecting each to the appropriate isomerization process that involves the methylation of toluene and/or
process maximizes the efficiency and effectiveness of the benzene to selectively produce PX, wherein streams having
process. At least part of the first isomerized stream is then differing amounts of ethylbenzene are separately treated to
recycled to the first PX adsorption section or optionally the increase the efficiency of the recovery of PX. With reference
first xylenes fractionation tower, and at least part of the to FIG. 2, a first hydrocarbon feed 102 comprising xylenes
second isomerized stream is then recycled to the second PX and EB is provided to a first para-Xylene adsorption section
adsorption section or optionally the second Xylenes fraction 130, where a first PX-rich stream 132 and a first PX-depleted
ation tower, to recover additional PX. The process is then stream 134 are recovered from the feed. A second hydro
repeated to define a so-called Xylene isomerization loop. carbon feed 104 comprising xylenes and less EB than the
0011. The invention also includes an apparatus for prac first hydrocarbon feed 102 is provided to a second para
ticing the inventive process comprising a first PX adsorption xylene adsorption section 140, where a second PX-rich
section, which produces a first PX-rich stream and a first stream 142 and a second PX-depleted stream 144 are
PX-depleted stream from a first hydrocarbon feed, and a recovered from the feed. The first and second PX-depleted
second PX adsorption section, which produces a second streams 134, 144 are then separated into an EB-rich stream
PX-rich stream and a second PX-depleted stream from a 172 and an EB-depleted stream 174 in a divided wall
second hydrocarbon feed. The first and second PX adsorp raflinate column 170. At least part of the EB-rich stream 172
tion sections are fluidly connected to a divided wall raflinate is then fed to a xylene isomerization unit 180 where the
column in which the first and second PX-depleted streams EB-rich stream 172 is isomerized under at least partial vapor
are separated into an EB-rich stream and an EB-depleted phase conditions to produce a first isomerized stream 182
stream. Fluidly connected to the divided wall raffinate having a higher PX concentration than the first and second
column is a vapor phase isomerization unit that isomerizes PX-depleted streams 134, 144. At least part of the EB
the EB-rich stream and produces a first isomerized stream depleted stream 174 is then fed to a xylene isomerization
having a higher PX concentration than the first and second unit 190 where the EB-depleted stream 174 is isomerized
PX-depleted streams, and a liquid phase isomerization unit under at least partial liquid phase conditions to produce a
that isomerizes the EB-depleted stream and produces a second isomerized stream 192 having a higher PX concen
second isomerized stream having a higher PX concentration tration than the first and second PX-depleted streams 134,
than the first and second PX-depleted streams. In embodi 144. At least part of the first isomerized stream 182 is then
US 2017/0050899 A1 Feb. 23, 2017

recycled to the first para-xylene adsorption section 130, and 0023 Depending on the composition of the first and
at least part of the second isomerized stream 192 is then second hydrocarbon feeds 102, 104, one or more initial
recycled to the second para-Xylene adsorption section 140, separation steps that serve to remove C7- and Co+ hydro
to recover additional PX and the process is repeated to define carbons from the feed may occur prior to providing the first
a so-called Xylene isomerization loop. and second hydrocarbon feeds 102, 104 to the first and
second para-xylene adsorption sections 130, 140. Generally,
Hydrocarbon Feed the initial separation steps may include fractional distilla
0019. The first hydrocarbon feed 102 employed in the tion, crystallization, adsorption, a reactive separation, a
present process may be any hydrocarbon stream containing membrane separation, extraction, or any combination
xylenes and EB, such as, but not limited to, a reformate thereof In one embodiment, the first hydrocarbon feed 102
stream (product stream of a reformate splitting tower), a is passed through a first xylenes fractionation tower 110
hydrocracking product stream, a Xylene or EB reaction prior to passing to the first para-Xylene adsorption section
product stream, an aromatic disproportionation stream, an 130. The first xylenes fractionation tower 110 produces a
aromatic transalkylation stream, a CyclarTM process stream, first overhead stream 112 comprising Cs hydrocarbons,
and/or an import stream. The first feed 102 may contain at which is sent to the first para-xylene adsorption section 130,
least 1.0 wt %, 2.0 wt %, 3.0 wt %, 5.0 wt %, 7.5 wt % or and a first bottoms stream 114 containing Co. hydrocarbons,
1O.O wit 9% EB. which may be sent to a transalkylation unit (not shown).
0020. The second hydrocarbon feed 104 may be a hydro 0024 Likewise, the second hydrocarbon feed 104 is
carbon stream containing Xylenes and less EB than the first passed through a second Xylenes fractionation tower 120
hydrocarbon feed 102, such as, but not limited to, a PX prior to passing to the second para-Xylene adsorption section
selective aromatic alkylation product stream, a non-selective 140. The second Xylenes fractionation tower 120 produces a
(equilibrium PX) aromatic alkylation product stream, an second overhead stream 122 comprising Cs hydrocarbons,
aromatic disproportionation stream, an aromatic transalky which is sent to the second para-Xylene adsorption section
lation stream, a methanol/dimethyl ether to aromatic product 140, and a second bottoms stream 124 containing Co.
stream, a syngas to aromatic product stream, a C-C, hydrocarbons. The second hydrocarbon feed 104 may be
alkane/alkene to aromatic product stream, an import stream, Subjected to phenol and styrene removal steps, such as those
described in U.S. Patent Publication Nos. 2013/0324779 and
and/or an off-spec PX stream from a PX recovery unit. The 2013/0324780, the entire contents of which are incorporated
second feed 104 may contain less than 10.0 wt %, 7.5 wt %, herein by reference, prior or Subsequent to the second
5.0 wt %, 3.0 wt %, 2.0 wt % or 1.0 wt % EB, as long as it xylenes fractionation tower 120. The second bottoms stream
is less than the EB content of the first feed 102.
0021. In one embodiment, the second hydrocarbon feed 124 may also be subjected to phenol and styrene removal
104 is the product of the selective alkylation of benzene steps, such as those described in U.S. Patent Publication
and/or toluene with methanol and/or dimethyl ether in a Nos. 2013/0324779 and 2013/0324780, before passing to a
methylation reactor. The reactor may be a fluidized bed, transalkylation unit (not shown), optionally with first bot
toms Stream 114.
moving bed, fixed bed, cyclic, or any combination thereof 0025 Depending on the material balance and equipment
One fluidized bed methylation reactor is described in U.S. requirements, a portion of the first hydrocarbon feed 102
Pat. Nos. 6,423,879 and 6,504,072, the entire contents of may be combined with the second hydrocarbon feed 104, or
which are incorporated herein by reference, and employs a Vice versa, prior to the Xylenes fractionator. Likewise, a
catalyst comprising a porous crystalline material having a
Diffusion Parameter for 2.2 dimethylbutane of about 0.1-15 portion of the overhead stream 112 may be combined with
sec' when measured at a temperature of 120° C. and a 2.2 the overhead stream 122, or vice versa, prior to the PX
dimethylbutane pressure of 60 torr (8 kPa). The porous adsorption sections 130, 140.
crystalline material may be a medium-pore Zeolite, such as Para-Xylene Recovery
ZSM-5, which has been severely steamed at a temperature
of at least 950° C. in the presence of at least one oxide (0026. The first hydrocarbon feed 102, or the first over
modifier, for example, including phosphorus, to control head stream 112 comprising Cs hydrocarbons in embodi
reduction of the micropore volume of the material during the ment in which first Xylenes fractionator is used, is Supplied
steaming step. An example of a fixed bed process and to a first para-xylene adsorption section 130 to produce a
catalyst is described in U.S. Pat. Nos. 7,304,194 and 8,558, first PX-rich product stream 132 and a first PX-depleted
046, which disclose a phosphorus-modified ZSM-5 catalyst stream 134. The second hydrocarbon feed 104, or the second
steamed at a temperature of 150-350° C. to increase selec overhead stream 122 comprising Cs hydrocarbons in
tivity to para-Xylene. embodiment in which second Xylenes fractionator is used, is
0022. The feeds may further comprise recycle stream(s) Supplied to a second para-Xylene adsorption section 140 to
from the isomerization step(s) and/or various separating produce a second PX-rich product stream 142 and a second
steps. The hydrocarbon feed comprises PX, together with PX-depleted stream 144. In one embodiment, the first and
MX, OX, and EB. In addition to xylenes and EB, the second PX-rich product streams 132, 142 comprise at least
hydrocarbon feedstock may also contain certain amounts of 10 wt % PX, preferably at least 50 wt % PX, more preferably
other aromatic or even non-aromatic compounds. Examples at least 70 wt % PX, even more preferably at least 80 wt %
of Such aromatic compounds are C7-hydrocarbons, such as PX, most preferably at least 90 wt % PX, and ideally at least
benzene and toluene, and C+ aromatics, such as mesitylene, 95 wt % PX, based on the total weight of the PX rich product
pseudo-cumene and others. These types offeedstream(s) are Stream.
described in “Handbook of Petroleum Refining Processes'. 0027. The first and second para-xylene adsorption sec
Eds. Robert A. Meyers, McGraw-Hill Book Company, Sec tions 130, 140 are preferably simulated moving bed adsorp
ond Edition. tion units, such as a PAREXTM unit or an ELUXYLTM unit.
US 2017/0050899 A1 Feb. 23, 2017

These types of separation unit(s) and their designs are the dividing wall and one or more side draws located on the
described in “Perry's Chemical Engineers' Handbook”. Eds. opposing side, or an inlet on both sides of the divided wall
R. H. Perry, D. W. Green and J. O. Maloney, McGraw-Hill column and multiple draws from the top or bottom of the
Book Company, Sixth Edition, 1984, and the previously column, or any combination thereof.
mentioned “Handbook of Petroleum Refining Processes.” In 0031. In a particular embodiment, the dividing wall
a typical simulated moving bed adsorption unit, the adsor extends from the top of the column down to a tray on which
bent bed consisting of several sub-beds is contained within the EB concentration is low enough to provide an optimum
two adsorption towers connected in series. In one embodi ratio of low EB and high EB products, which is ascertainable
ment, the first para-Xylene adsorption section 130 and sec by one skilled in the art using simulation tools. The first
ond para-Xylene adsorption section 140 are separate simu PX-depleted stream 134 derived from the first hydrocarbon
lated moving bed adsorption units, having two adsorption feed 102 having a higher EB concentration is provided to the
towers in each section. In another embodiment, the first divided wall raffinate column 170 on one side of the dividing
para-Xylene adsorption section 130 and second para-Xylene wall, and the second PX-depleted stream 144 derived from
adsorption section 140 each comprise one tower of a single the second hydrocarbon feed 104 having a lower EB con
simulated moving bed adsorption unit. centration is provided to the divided wall raflinate column
0028 Treating feeds with differing EB contents, for 170 on the opposite side of the dividing wall. The EB-rich
example, feeds with less than 1.0 wt % EB and feeds with stream 172 and the EB-depleted stream 174 are withdrawn
more than 1.0 wt % EB, separately results in more efficient from the top of the column or near the top of the column to
adsorption of PX. While the adsorbent has a higher affinity remove lighter components such as water. Each overhead
for PX, it may also adsorb EB to a significant extent, thereby stream may be processed through a separate overhead prod
reducing the adsorbents capacity to adsorb PX. Thus, uct system (not shown), and a portion of the EB-rich stream
subjecting feeds with lower amounts of EB, i.e., less than 1.0 172 and EB-depleted stream 174 may be returned to the
wt % EB, to a separate PX adsorption section minimizes the divided wall raflinate column 170 as reflux. Using a divided
amount of EB competing for adsorption capacity and wall column as the raflinate column further enhances the EB
increases the efficiency of PX adsorption in that adsorption separation in the PX-depleted streams, allowing for more
section, leading to more efficient adsorption of PX overall. efficient use of isomerization processes.
0029. In FIG. 2, as in conventional simulated moving bed 0032. At least a portion of the EB-rich stream 172 is sent
plant configurations, the first and second PX-rich product to isomerization unit 180, and at least a portion of the
streams 132, 142, comprising PX and desorbent, are sent to EB-depleted stream 174 is sent to isomerization unit 190. In
an extract column 150 for separation, which produces a PX other embodiments in which the amount of EB in the
stream 152 and a first desorbent stream 154. The first EB-rich stream is minimal, the EB-rich stream may be
desorbent stream 154 is recycled to the first and second purged to fuel blending. The second desorbent stream 176 is
para-xylene adsorption sections 130, 140, optionally recycled to the first and second para-Xylene adsorption
through a desorbent drum. The PX stream 152 is then sent sections 130, 140, optionally through a desorbent drum.
to a finishing column 160, which produces a purified PX
product 162. A toluene stream 164 is recovered as an Xylene Isomerization
overheads product from the finishing column 160 and may
be recycled back to the PX production process, preferably 0033. Because liquid phase isomerization converts little
the selective alkylation of benzene and/or toluene with or none of the EB in the PX-depleted stream, in a preferred
methanol and/or dimethyl ether. In a conventional simulated embodiment, the EB-rich stream 172 is sent to isomerization
moving bed plant configuration, the PX-depleted streams, unit 180, which is operated in the vapor phase, and the
comprising MX, OX, EB, and desorbent, are sent to a EB-depleted stream 174 is sent to isomerization unit 190,
raftinate column; however, in the present process, a divided which is operated in the liquid phase. Minimizing the
wall raflinate column replaces the conventional raflinate amount of PX-depleted stream subjected to vapor phase
tower, which will be described below. isomerization saves energy and capital, as liquid phase
isomerization requires less energy and capital than the vapor
Divided Wall Raftinate Column phase isomerization process due to the requirement of
vaporizing the PX-depleted stream and the use of hydrogen,
0030. With continuing reference to FIG. 2, the first and which requires an energy- and capital-intensive hydrogen
second PX-depleted streams 134, 144 pass to a divided wall recycle loop.
raflinate column 170, replacing the conventional raflinate
column (fractionator 37 in FIG. 1), which separates the first Vapor Phase Isomerization
and second PX-depleted streams 134, 144 into three
streams—an EB-rich stream 172, an EB-depleted stream 0034. The EB-rich stream 172 is fed to a xylene isomer
174, and a second desorbent stream 176. As its name ization unit 180 where the EB-rich stream 172 is contacted
implies, the term “divided wall distillation column” refers to with a Xylene isomerization catalyst under at least partially
a particular known form of distillation column which com vapor phase conditions effective to isomerize the PX-de
prises a dividing wall. The dividing wall vertically bisects a pleted, EB-rich stream 172 back towards an equilibrium
portion of the interior of the distillation column but does not concentration of the Xylene isomers. There are generally two
extend either to the top or bottom sections of the column, types of vapor phase isomerization catalysts—one that
thus, enabling the column to be refluxed and reboiled similar dealkylates EB to produce benzene and ethylene and isomer
to a conventional column. The dividing wall provides a fluid izes the Xylene isomers, and one that isomerizes the four
impermeable baffle separating the interior of the column. different C8 aromatic compounds, including EB, to their
The divided wall column may be configured for a number of equilibrium concentrations. Either catalyst may be used for
processes, with an inlet to the column located on one side of the vapor phase isomerization unit 180.
US 2017/0050899 A1 Feb. 23, 2017

EB Dealkylation weight, e.g., from about 0.05 to about 5 percent by weight,

0035. In one embodiment, the EB-rich stream 172 is e.g., from about 0.1 to about 2 percent by weight of a
hydrogenation/dehydrogenation component. Examples of
subjected to xylenes isomerization in which the EB in the Such components include the oxide, hydroxide, Sulfide, or
stream can be dealkylated to produce benzene. In this free metal (i.e., Zero valent) forms of Group VIIIA metals
embodiment, where the ethylbenzene is removed by crack (i.e., Pt, Pd, Ir, Rh, Os, Ru, Ni, Co, and Fe), Group VIIA
ing/disproportionation, the para-Xylene-depleted Cs stream metals (i.e., Mn, Tc, and Re), Group VIA metals (i.e., Cr,
is conveniently fed to a multi-bed reactor comprising at least Mo, and W), Group VB metals (i.e., Sb and Bi), Group IVB
a first bed containing an ethylbenzene conversion catalyst metals (i.e., Sn and Pb), Group IIIB metals (i.e., Ga and In),
and a second bed downstream of the first bed and containing and Group IB metals (i.e., Cu, Ag and Au). Noble metals
a Xylene isomerization catalyst. The beds can be in the same (i.e., Pt, Pd, Ir, Rh, Os and Ru) are preferred hydrogenation/
or different reactors. Alternatively, the ethylbenzene conver dehydrogenation components. Combinations of catalytic
sion catalyst and Xylene isomerization catalyst may be forms of Such noble or non-noble metal. Such as combina
contained in a single bed reactor. tions of Pt with Sn, may be used. The metal may be in a
0036. The ethylbenzene conversion catalyst typically reduced Valence state, e.g., when this component is in the
comprises an intermediate pore size Zeolite having a Con form of an oxide or hydroxide. The reduced valence state of
straint Index ranging from 1 to 12, a silica to alumina molar this metal may be attained, in situ, during the course of a
ratio of at least about 5, such as at least about 12, for reaction, when a reducing agent, such as hydrogen, is
example at least 20, and an alpha value of at least 5. Such as included in the feed to the reaction.
75 to 5000. Constraint Index and its method of determina
tion are disclosed in U.S. Pat. No. 4,016, 218, which is 0041. The xylene isomerization catalyst employed in this
herein incorporated by reference, whereas the alpha test is embodiment typically comprises an intermediate pore size
described in U.S. Pat. No. 3,354,078 and in the Journal of Zeolite, e.g., one having a Constraint Index between 1 and
Catalysis, Vol. 4, p. 527 (1965); Vol. 6, p. 278 (1966); and 12, specifically ZSM-5. The acidity of the ZSM-5 of this
Vol. 61, p. 395 (1980), each incorporated herein by reference catalyst, expressed as the alpha value, is generally less than
as to that description. The experimental conditions of the test about 150, such as less than about 100, for example from
used herein include a constant temperature of 538°C. and a about 5 to about 25. Such reduced alpha values can be
variable flow rate as described in detail in the Journal of obtained by Steaming. The Zeolite typically has a crystal size
Catalysis, Vol. 61, p. 395. Higher alpha values correspond less than 0.2 micron and an ortho-Xylene sorption time Such
with a more active cracking catalyst. that it requires less than 50 minutes to sorb ortho-xylene in
0037 Examples of suitable intermediate pore size Zeo an amount equal to 30% of its equilibrium Sorption capacity
lites include ZSM-5 (U.S. Pat. Nos. 3,702,886 and Re. for ortho-xylene at 120° C. and a xylene pressure of 4.5+0.8
29,948); ZSM-11 (U.S. Pat. No. 3,709,979); ZSM-12 (U.S. mm of mercury. The Xylene isomerization catalyst may be
Pat. No. 3,832,449); ZSM-22 (U.S. Pat. No. 4,556,477); self-bound form (no binder) or may be composited with an
ZSM-23 (U.S. Pat. No. 4,076,842); ZSM-35 (U.S. Pat. No. inorganic oxide binder, Such as alumina. In addition, the
4,016,245); ZSM-48 (U.S. Pat. No. 4,397,827); ZSM-57 Xylene isomerization catalyst may contain the same hydro
genation/dehydrogenation component as the ethylbenzene
(U.S. Pat. No. 4,046,685); ZSM-58 (U.S. Pat. No. 4,417, conversion catalyst.
780); EU-1; and mordenite. The entire contents of the above 0042. Using the catalyst system described above, ethyl
references are incorporated by reference herein. Preferred benzene cracking/disproportionation and Xylene isomeriza
Zeolites are ZSM-5, ZSM-12 or EU-1. tion are typically effected at conditions including a tempera
0038. The Zeolite employed in ethylbenzene conversion
catalyst typically has a crystal size of at least 0.2 microns ture of from about 400° F to about 1,000° F (204 to 538°
and exhibits an equilibrium Sorption capacity for Xylene, C.), a pressure of from about 0 to about 1,000 psig (100 to
which can be either para, meta, ortho, or a mixture thereof, 7,000 kPa), a weight hourly space velocity (WHSV) of
of at least 1 gram per 100 grams of Zeolite measured at 120° between about 0.1 and about 200 hr-1, and a hydrogen, H.
C. and a xylene pressure of 4.5+0.8 mm of mercury and an to hydrocarbon, HC, molar ratio of between about 0.1 and
ortho-xylene sorption time for 30 percent of its equilibrium about 10. Alternatively, the conversion conditions may
ortho-Xylene sorption capacity of greater than 1200 minutes include a temperature of from about 650° F. and about 900°
(at the same conditions of temperature and pressure). The F. (343 to 482°C.), a pressure from about 50 and about 400
Sorption measurements may be carried out gravimetrically in psig (446 to 2,859 kPa), a WHSV of between about 3 and
a thermal balance. The sorption test is described in U.S. Pat. about 50 hr-1 and a H to HC molar ratio of between about
Nos. 4,117,026; 4,159,282; 5,173,461; and Re. 31,782, each 0.5 and about 5. The WHSV is based on the weight of
of which is incorporated by reference herein. catalyst composition, i.e., the total weight of active catalyst
0039. The Zeolite used in the ethylbenzene conversion plus, if used, binder therefor.
catalyst may be self-bound (no binder) or may be compos EB Isomerization
ited with an inorganic oxide binder, with the Zeolite content
ranging from between about 1 to about 99 percent by weight 0043. In another embodiment, the EB-rich stream 172 is
and more usually in the range of about 10 to about 80 percent Subjected to EB isomerization to produce a stream contain
by weight of the dry composite, e.g., about 65% zeolite with ing the Cs aromatic compounds in equilibrium concentra
about 35% binder. Where a binder is used, it is preferably tions.
non-acidic, such as silica. Procedures for preparing silica 0044) Typically, the EB isomerization catalyst comprises
bound ZSM-5 are described in U.S. Pat. Nos. 4,582,815; an intermediate pore size molecular sieve having a Con
5,053,374; and 5,182.242, incorporated by reference herein. straint Index within the approximate range of 1 to 12, Such
0040. In addition, the ethylbenzene conversion catalyst as ZSM-5 (U.S. Pat. No. 3,702,886 and Re.29,948); ZSM
typically comprises from about 0.001 to about 10 percent by 11 (U.S. Pat. No. 3,709,979); ZSM-12 (U.S. Pat. No. 3,832,
US 2017/0050899 A1 Feb. 23, 2017

449); ZSM-22 (U.S. Pat. No. 4,556,477); ZSM-23 (U.S. Pat. 0049. The conditions employed in the EB isomerization
No. 4,076,842); ZSM-35 (U.S. Pat. No. 4,016,245); ZSM-48 process generally include a temperature of from 300 to about
(U.S. Pat. No. 500° C., preferably from about 320 to about 450° C. and
0045 4,397,827); ZSM-57 (U.S. Pat. No. 4,046,685); more preferably from about 340 to about 430° C.; a partial
and ZSM-58 (U.S. Pat. No. 4,417,780). Alternatively, the pressure of hydrogen from about 0.3 to about 1.5 MPa,
Xylene isomerization catalyst may comprise a molecular preferably from about 0.4 to about 1.2 MPa, and more
sieve selected from MCM-22 (described in U.S. Pat. No. preferably from about 0.7 to about 1.2 Mpa; a total pressure
4.954.325); PSH-3 (described in U.S. Pat. No. 4,439.409): of from about 0.45 to about 1.9 MPa, preferably from about
SSZ-25 (described in U.S. Pat. No. 4,826,667); MCM-36 0.6 to about 1.5 MPa.; and a weight hourly space velocity
(described in U.S. Pat. No. 5.250,277); MCM-49 (described (WHSV) of between about 0.25 and about 30 hr', prefer
in U.S. Pat. No. 5,236,575); and MCM-56 (described in U.S. ably between about 1 and about 10 hr' and more preferably
Pat. No. 5,362.697). The molecular sieve may also comprise between about 2 and about 6 hr'.
a EUO structural type molecular sieve, with EU-1 being 0050. The product of the vapor phase xylene isomeriza
preferred, or mordenite. A preferred molecular sieve is one tion process 180 is a first isomerized stream 182 having a
of the EUO structural type having a Si/A1 ratio of about higher PX concentration than the first and second PX
10-25, as disclosed in U.S. Pat. No. 7,893,309. The entire depleted streams 134, 144. The first isomerized stream 182
contents of the above references are incorporated by refer is then recycled to the first para-Xylene adsorption section
ence herein. 130 to recover additional PX and the process is repeated to
0046. It may be desirable to combine the molecular sieve generate a so-called Xylene isomerization loop. In embodi
of the xylene isomerization catalyst with another material ments, the first isomerized stream 182 is passed through a
resistant to the temperature and other conditions of the detoluenizing fractionation column 184 to produce at least
process. Such matrix materials include synthetic or naturally one C7 isomerized stream and a Cs isomerized stream 186,
occurring Substances as well as inorganic materials such as which is passed through the first Xylenes fractionation
clay, silica, and/or metal oxides (such as titanium oxide or column 110, before being recycled to the first para-xylene
boron oxide). The metal oxides may be naturally occurring adsorption section 130 to recover additional PX. Preferably,
or in the form of gelatinous precipitates or gels including the detoluenizing fractionation column 184 produces two
mixtures of silica and metal oxides. Naturally occurring Cz isomerized streams—a benzene and/or toluene stream
clays, which can be composited with the molecular sieve, 187 that may be sent to extraction and a light ends/hydrogen
include those of the montmorillonite and kaolin families, stream 189 that may be sent to fuel.
which families include the subbentonites and the kaolins
commonly known as Dixie, McNamee, Georgia, and Florida Liquid Phase Isomerization
clays or others in which the main mineral constituent is 0051. The EB-depleted stream 174 is fed to a xylene
halloysite, kaolinite, dickite, nacrite, oranauxite. Such clays isomerization unit 190 where the EB-depleted stream 174 is
can be used in the raw state as originally mined or initially contacted with a Xylene isomerization catalyst under at least
Subjected to calcination, acid treatment, or chemical modi partially liquid phase conditions effective to isomerize the
fication. PX-depleted, EB-depleted stream 174 back towards an equi
0047. In addition to the foregoing materials, the molecu librium concentration of the xylene isomers. Suitable con
lar sieve may be composited with a porous matrix material, ditions for the liquid phase isomerization include a tempera
Such as alumina, Zirconia, silica-alumina, Silica-magnesia, ture of from about 200° C. to about 540° C., preferably from
silica-Zirconia, silica-thoria, silica-berylia, silica-titania, alu about 230° C. to about 310° C., and more preferably from
minum phosphates, titanium phosphates, Zirconia phos about 270° C. to about 300° C., a pressure of from about 0
phates, as well as ternary compounds such as silica-alumina to 6,895 kPa (g), preferably from about 1,300 kPag) to about
thoria, silica-alumina-Zirconia, silica-alumina-magnesia, 3,500 kPa (g), a weight hourly space velocity (WHSV) of
and silica-magnesia-Zirconia. A mixture of these compo from 0.5 to 100 hr', preferably from 1 to 20 hr', and more
nents could also be used. The matrix may be in the form of preferably from 1 to 10 hr'. Generally, the conditions are
a cogel. The relative proportions of molecular sieve com selected so that a portion, preferably at least 25 wt %, and
ponent and inorganic oxide gel matrix on an anhydrous basis more preferably at least 50 wt %, and ideally 100 wt % of
may vary widely with the molecular sieve content ranging the Cs aromatics would be expected to be in the liquid phase.
from between about 1 to about 99 percent by weight and Low levels of hydrogen, below the solubility limit, may be
more usually in the range of about 10 to about 80 percent by added to the liquid phase isomerization process.
weight of the dry composite. 0.052 Any catalyst capable of isomerizing xylenes in the
0048. The EB isomerization catalyst also comprises at liquid phase can be used in the Xylene isomerization unit, but
least one metal from Group VIII of the periodic table of the in one embodiment the catalyst comprises an intermediate
elements and optionally at least one metal selected from pore size Zeolite having a Constraint Index between 1 and
metals from Groups IIIA, IVA, and VIIB. The Group VIII 12. Constraint Index and its method of determination are
metal present in the catalyst used in the isomerization described in U.S. Pat. No. 4,016,218, which is incorporated
process of the invention is selected from iron, cobalt, nickel, herein by reference. Particular examples of suitable inter
ruthenium, rhodium, palladium, osmium, iridium, and plati mediate pore size Zeolites include ZSM-5, ZSM-11, ZSM
num, preferably from the noble metals and highly preferably 12, ZSM-22, ZSM-23, ZSM-35, ZSM-48, and MCM-22,
from palladium and platinum. More preferably, the Group with ZSM-5 and ZSM-11 being particularly preferred, spe
VIII metal is platinum. The metal selected from groups IIIA, cifically ZSM-5. It is preferred that the acidity of the Zeolite,
IVA, and VIIB which are optionally present is selected from expressed as its alpha value, be greater than 300, such as
gallium, indium, tin, and rhenium, preferably from indium, greater than 500, or greater than 1,000. The alpha test is
tin, and rhenium. described in U.S. Pat. No. 3,354,078; in the Journal of
US 2017/0050899 A1 Feb. 23, 2017

Catalysis, Vol. 4, p. 527 (1965); Vol. 6, p. 278 (1966); and alkylation product stream, an aromatic disproportionation
Vol. 61, p. 395 (1980), each incorporated herein by reference stream, an aromatic transalkylation stream, an off-spec PX
as to that description. The experimental conditions of the test stream from a PX recovery unit, an intermediate stream from
used to determine the alpha values cited herein include a a crystallizer unit, and/or an import stream.
constant temperature of 538°C. and a variable flow rate as 0057 The divided wall xylenes fractionation column 210
described in detail in the Journal of Catalysis, Vol. 61, p. separates the feeds 202, 204 into three streams—an equi
395. A preferred catalyst is described in U.S. Pat. No. librium PX stream 212, an enhanced PX stream 214, and a
8,569,559, which is incorporated herein by reference. bottoms stream 216 containing Co. hydrocarbons. The bot
0053. The product of the liquid phase xylene isomeriza toms stream 216 containing Co. hydrocarbons may be sent
tion unit 190 is a second isomerized stream 192 having a to a transalkylation unit to produce additional benzene,
higher PX concentration than the first and second PX toluene and/or xylenes. The equilibrium PX stream 212 and
depleted streams 134, 144. The second isomerized stream enhanced PX stream 214 are provided to a PX recovery unit
192 is then recycled to first para-xylene adsorption section 230, preferably a simulated moving bed adsorption unit,
130 or second para-xylene adsorption section 140 to recover which produces a PX-rich product stream 232 and a PX
additional PX and the process is repeated to generate a depleted stream 234. The PX-rich product stream 232,
so-called Xylene isomerization loop. To manage the level of comprising PX and desorbent, is sent to an extract column
EB in the liquid phase isomerization loop and prevent a 250 for separation, which produces a PX stream 252 and a
buildup of EB, a purge stream 194 may be removed from desorbent stream 254. The desorbent stream 254 is recycled
upstream or downstream of the liquid phase Xylene isomer to the PX recovery unit 230, optionally through a desorbent
ization unit 190 at regular intervals (which may be deter drum. The PX stream 252 is then sent to a finishing column
mined by one skilled in the art) and passed to the xylene 260, which produces a purified PX product 262. A toluene
isomerization unit 180 where the EB may be converted. stream 264 is recovered as an overheads product from the
0054 Conducting xylenes isomerization under liquid finishing column 260 and may be recycled back to the PX
phase conditions produces less C aromatics than xylenes production process, preferably the selective alkylation of
isomerization under vapor phase conditions. Therefore, the benzene and/or toluene with methanol and/or dimethyl ether.
second isomerized stream 192 may be provided to the In a conventional simulated moving bed plant configuration,
second Xylenes fractionation tower 120 at a higher tray the PX-depleted streams, comprising MX, OX, EB, and
location than the second hydrocarbon feed 104, yielding desorbent, are sent to a raftinate column; however, in the
greater energy savings. Furthermore, a significant portion of present process, a divided wall raflinate column replaces the
the second isomerized stream 192 may bypass the second conventional raflinate tower.
xylenes fractionation tower 120 and directly enter the sec 0058. The PX-depleted stream 234 passes to a divided
ond para-Xylene adsorption section 140, thereby saving wall raflinate column 270, replacing the conventional raffi
energy by avoiding the re-fractionation altogether. nate column (fractionator 37 in FIG. 1), which separates the
0055. In situations where only a single simulated moving PX-depleted stream 234 into three streams—an EB-rich
bed unit is used conventionally, or where it is not feasible to stream 272, an EB-depleted stream 274, and a desorbent
segregate feeds with differing levels of EB, it is advanta stream 276. At least a portion of the EB-rich stream 272 is
geous to segregate high PX feeds and low PX feeds as taught sent to isomerization unit 280, which is operated in the vapor
in U.S. Pat. Nos. 5,750,820 and 8,529,757, the entire con phase, and at least a portion of the EB-depleted stream 274
tents of the above references are incorporated by reference is sent to isomerization unit 290, which is operated in the
herein. In order to provide high PX feeds separately from liquid phase. The desorbent stream 276 is recycled to the PX
low PX feeds to the PX recovery unit and avoid the use of recovery unit 230, optionally through a desorbent drum.
separate Xylenes fractionation columns, a divided wall col 0059. The product of the vapor phase xylene isomeriza
umn may be used. tion unit 280 is a vapor-phase isomerized stream 282 having
0056. In the embodiment shown in FIG. 3, a hydrocarbon a higher PX concentration than the PX-depleted stream 234.
feed 202 containing equilibrium Xylenes is provided to a The vapor-phase isomerized stream 282 is then recycled to
divided wall xylenes fractionation column 210 and a hydro the PX recovery unit 230 to recover additional PX and the
carbon feed 204 containing PX in an amount higher than its process is repeated to generate a so-called Xylene isomer
equilibrium concentration is provided to the column 210 on ization loop. In embodiments, the vapor-phase isomerized
other side of the dividing wall. The feed 204 may be stream 282 is passed through a detoluenizing fractionation
Supplied at a higher tray position due to its higher concen column 284 to produce at least one C7 isomerized stream
tration of PX or to its lower concentration of Caromatics, and a Cs isomerized stream 286, which is passed through
typically found in toluene methylation or toluene dispropor the divided wall xylenes fractionation column 210, before
tionation product streams, which may be determined by one being recycled to the PX recovery unit 230 to recover
skilled in the art. The feed 202 may be any hydrocarbon additional PX. Preferably, the detoluenizing fractionation
stream containing Xylenes in their equilibrium concentra column 284 produces two Cz isomerized streams—a ben
tions, i.e., about 22-24 wt % PX, such as a reformate stream Zene and/or toluene stream 287 that may be sent to extrac
(product stream of a reformate splitting tower), a hydroc tion and a light ends/hydrogen stream 289 that may be sent
racking product stream, a Xylene or EB reaction product to fuel.
stream, an aromatic disproportionation stream, an aromatic 0060. The product of the liquid phase xylene isomeriza
transalkylation stream, a non-selective aromatic alkylation tion unit 290 is a liquid-phase isomerized stream 292 having
product stream, a methanol to aromatic product stream, a a higher PX concentration than the PX-depleted stream 234.
CyclarTM process stream, and/or an import stream. The feed The liquid-phase isomerized stream 292 is then recycled to
204 may be a hydrocarbon stream containing more than the PX recovery unit 230 to recover additional PX and the
about 22-24 wt % PX, such as a PX selective aromatic process is repeated to generate a so-called Xylene isomer
US 2017/0050899 A1 Feb. 23, 2017

ization loop. To manage the level of EB in the liquid phase crystallizer 520 at about -80° F. with ethylene refrigeration
isomerization loop and prevent a buildup of EB, a purge produces a filtrate 524 with about 10 wt % PX and about 4-5
stream 294 may be removed from upstream or downstream wt % of EB.
of the liquid phase xylene isomerization unit 290 at regular 0065. If the filtrate 524 contains less than about 22-24 wit
intervals (which may be determined by one skilled in the art) % PX, such as when ethylene refrigeration is used, then the
and passed to the xylene isomerization unit 280 where the filtrate 524 is sent to the liquid phase isomerization unit 290
EB may be converted. The liquid-phase isomerized stream to isomerize the xylenes. If the filtrate 524 contains more
292 may first pass through the divided wall xylenes frac than about 22-24 wt % PX, such as when propylene refrig
tionation column 210, on either side of the dividing wall, or eration is used, then the filtrate 524 is sent to the divided wall
be provided to the PX recovery unit 230 with either the Xylenes fractionation column 210. The remaining steps
follow the embodiments shown in FIGS. 3 and 5. The PX
equilibrium PX stream 212 or enhanced PX stream 214. recovery section of FIG. 5, depicted as PX recovery unit
0061 FIG. 4 depicts an embodiment in which a divided 230, may follow the single PX recovery unit embodiment as
wall Xylenes fractionation column is used in conjunction shown in FIG. 3 or the two section PX recovery unit
with two PX adsorption sections. Corresponding elements embodiment as shown in FIG. 4.
from FIG. 3 use the same reference numerals in FIG. 4. A 0.066 While the present invention has been described and
hydrocarbon feed 202 containing equilibrium Xylenes is illustrated by reference to particular embodiments, those of
provided to a divided wall xylenes fractionation column 210 ordinary skill in the art will appreciate that the invention
and a hydrocarbon feed 204 containing PX in an amount lends itself to variations and modification is not necessarily
higher than its equilibrium concentration is provided to the illustrated herein without departing from the spirit and scope
column 210 on other side of the dividing wall. The divided of the invention.
wall xylenes fractionation column 210 separates the feeds 0067. Trade names used herein are indicated by a TM
202, 204 into three streams—an equilibrium PX stream 212, symbol or (R) symbol, indicating that the names may be
an enhanced PX stream 214, and a bottoms stream 216 protected by certain trademark rights, e.g., they may be
containing Cohydrocarbons. registered trademarks in various jurisdictions. All patents
0062. The equilibrium PX stream 212 is provided to a and patent applications, test procedures (such as ASTM
first PX recovery unit 230, preferably a simulated moving methods, UL methods, and the like), and other documents
bed adsorption unit, which produces a PX-rich product cited herein are fully incorporated by reference to the extent
Such disclosure is not inconsistent with this invention and
stream 232 and a PX-depleted stream 234. The enhanced PX for all jurisdictions in which Such incorporation is permitted.
stream 214 is provided to a first PX recovery unit 240, When numerical lower limits and numerical upper limits are
preferably a simulated moving bed adsorption unit, which listed herein, ranges from any lower limit to any upper limit
produces a PX-rich product stream 242 and a PX-depleted are contemplated.
stream 244. The PX-rich product streams 232, 242, com
prising PX and desorbent, are sent to an extract column 250 1.-15. (canceled)
for separation, and the PX-depleted streams 234, 244 pass to 16. An apparatus for the production of para-Xylene com
a divided wall raftinate column 270. The remainder of the prising:
steps are similar to those described above with FIG. 3. a first para-Xylene adsorption section, which produces a
first para-Xylene-rich stream and a first para-Xylene
0063 FIG. 5 depicts an embodiment in which a crystal depleted stream from a first hydrocarbon feed, and a
lizer is used to recover PX from the product of the selective second para-Xylene adsorption section, which produces
alkylation of benzene and/or toluene with methanol and/or a second para-Xylene-rich stream and a second para
dimethyl ether. Corresponding elements from FIGS. 3 and 4 Xylene-depleted stream from a second hydrocarbon
use the same reference numerals in FIG. 5. A product stream feed, the first and second para-Xylene adsorption sec
502 from the selective alkylation of benzene and/or toluene tions fluidly connected to a divided wall raffinate
with methanol and/or dimethyl ether in a methylation reactor column in which the first and second para-Xylene
is provided to a toluene fractionation tower 510, to which a depleted streams are provided to opposite sides of the
fresh toluene 504 may also be provided. The toluene frac dividing wall and separated into an ethylbenzene-rich
tionation tower produces an overhead toluene stream 506 stream, which contains a majority portion of the eth
that is recycled back to the methylation reactor (not shown) ylbenzene from the first and second para-Xylene-de
and a Cs bottoms stream 508 that is provided to a crystal pleted streams, and an ethylbenzene-depleted stream,
lizer 520. The Cs bottoms stream 508 may contain C. which contains a minor portion of the ethylbenzene
aromatics, such as trimethylbenzene, methylethylbenzene, from the first and second para-Xylene-depleted streams;
tetramethylbenzene, naphthalene, and heavy oxygenates, a vapor phase isomerization unit fluidly connected to the
but as taught by U.S. Pat. No. 8,907,152, the Cs bottoms divided wall raflinate column to isomerize meta-xy
stream 508 may contain up to 10 wt % Caromatics before lene, ortho-xylene, and ethylbenzene in the ethylben
necessitating fractionation upstream of the crystallizer 520. Zene-rich stream at least partially in the vapor phase
Optionally, Cs, bottoms stream 508 may be provided to the back towards to an equilibrium concentration of Xylene
divided wall xylenes fractionation column 210. isomers and produce a first isomerized stream having a
0064. The crystallizer 520 may be operated at about -20° higher para-Xylene concentration than the first and
F. with propylene refrigeration or about -80° F. with ethyl second para-Xylene-depleted streams; and
ene refrigeration, as may be determined by one skilled in the a liquid phase isomerization unit fluidly connected to the
art. Operating the crystallizer 520 at about -20° F. with divided wall raffinate column to isomerize the ethyl
propylene refrigeration produces a filtrate 524 with about 30 benzene-depleted stream back towards an equilibrium
wt % PX and about 3-4 wt % of EB, while operating the concentration of the Xylenes isomers and produce a
US 2017/0050899 A1 Feb. 23, 2017

second isomerized stream having a higher para-Xylene

concentration than the first and second para-Xylene
depleted streams.
17. The apparatus of claim 16, wherein the first and
second para-Xylene adsorption sections each comprise two
simulated moving bed adsorption towers.
18. The apparatus of claim 16, wherein the first and
second para-Xylene adsorption sections each comprise one
simulated moving bed adsorption tower.
19. The apparatus of claim 16, further comprising:
a first Xylenes fractionation column fluidly connected to
the vapor phase isomerization unit and the first para
Xylene adsorption section, wherein the first Xylenes
fractionation column is downstream of the vapor phase
isomerization unit and upstream of the first para-Xylene
adsorption section; and
a second Xylenes fractionation column fluidly connected
to the liquid phase isomerization unit and the second
para-Xylene adsorption section, wherein the second
Xylenes fractionation column is downstream of the
liquid phase isomerization unit and upstream of the
second para-Xylene adsorption section.
20. The apparatus of claim 19, further comprising a
detoluenizing fractionation column fluidly connected to the
vapor phase isomerization unit and the first Xylenes frac
tionation column, wherein the detoluenizing fractionation
column is downstream of the vapor phase isomerization unit
and upstream of the first Xylenes fractionation column.