Alternative routes to paraxylene

production
An integrated refining and petrochemical approach to paraxylene manufacture from
various feedstocks, such as excess aromatics in reformate or pyrolysis gasoline

Jacques Rault, Christian Dupraz and Françoise Montecot Axens

A
n annual market growth of 6% to 8% over applications. Further into this article, a repre-
the next decade is forecast for paraxylene sentative paraxylene production complex is
(PX), which is the main building block for reviewed and the features of its component units
an increasingly diverse range of polyethylene are described.
terephthalate (PET) resin and fibre consumer An examination of three alternative PX process
products. Increasing demand is a welcome schemes follows. The first two alternatives take
change for a PX industry recovering from years advantage of existing captive aromatics streams,
of overcapacity and severe economic woes in whereas the third alternative reviews an
Asia. Although the way to demand
growth is clear, the industry wants
reduced investment routes to PX Raffinate

and benzene. More importantly, the Benzene

industry will be examining potential
synergies between petrochemicals Toluene
H2 Extraction:
and refining.
• Morphylane
In recent years, PX overcapacity C7–
• Sulfolane
and economic turmoil in Asia Aromizing
combined to diminish PX industry & Arofining
profitability. However, according to
multi-client studies, PX demand Tol–A9–A10
should be applying pressure on Transalkylation
Naphtha
TransPlus
existing or scheduled capacity in the hydrotreater
coming years. In configuring the Paraxylene
emerging new grassroots projects,
C8+
refiners and petrochemical produc- Naphtha C8A isom.
Px
ers are benefiting from new separation • Oparis
developments and the experience Eluxyl • XyMax C9+C10
acquired over the past few years.
High, single-train capacity is a
straightforward way to reduce capi-
tal cost and benefit from economies
of scale. By examining aromatics
availability and needs in other areas Heavy
C9+ aromatics
of refinery or petrochemical
complexes, a PX manufacturer can
find ways to divert the investment Figure 1 Aromatics complex representing a configuration typical of the
burden towards several value-added mid-1990s

www.digitalrefining.com/article/1000279 PTQ Q2 2004 1

 production, the reforming reactions take
Regenerator
place at high temperatures and low pres-
sures using a highly selective and robust
catalyst (AR 501) and Axens’ CCR technol-
Reactors ogy. This unit is similar in function and
and heaters
layout to its gasoline CCR reforming coun-
terpart known as Octanizing. The
continuous catalyst circulation loop employs
a series of lift lines that convey catalyst
beads from the bottom of one reactor to the
top of the next reactor (Figure 2).
Many attractive features arise from the
side-by-side reactor arrangement: simpler
reactor designs, low-profile structures,
Booster reduced engineering costs and easier
compressor H2 rich gas
construction. For example, reactor wall
thickness depends on process conditions
rather than on thermal expansion or
Recovery
system mechanical constraints. The side-by-side
arrangement also allows the heaters to be
positioned directly in front of each reactor,
Feed To resulting in short transfer lines, reduced
stabilisation mechanical and thermal constraints and a
Recycle compact, low-cost implantation.
compressor The catalyst circulation and regeneration
system is fully automated and ensures very
Figure 2 Simplified Aromizing flow scheme low catalyst consumption from attrition as
well as stable performance during catalyst
integrated grassroots refinery-petrochemicals life. Catalyst life up to nine years has been
scheme. industrially achieved.
The paraxylene production scheme displayed
in Figure 1 can be considered as representative PX separation/purification and C8 isomerisation
of complexes erected in the mid-1990s. The prin- The effluent from the aromatics unit is distilled
cipal operating units perform the following into C7- and C8+ fractions. The C8+ cut is further
functions: aromatics “backbone” production distilled into C8 aromatics and C9+ streams. The
from naphtha by high severity reforming, PX xylenes are sent to the xylenes loop, which uses
separation and purification, C8 raffinate isomeri- the proprietary Eluxyl technology for PX separa-
zation, toluene and C9-C10 transalkylation, and tion and purification. There are two process
benzene-toluene extractive distillation. The prin- versions, stand-alone and hybrid, each able to
cipal products are PX, benzene and hydrogen. produce the general PX purity requirement of
Processing commences with a hydrotreated 99.9%. The stand-alone version employs two
naphtha heart cut feed to the proprietary adsorption columns whereas the hybrid version
Aromizing reformer, which yields a full range of uses one column followed by a single stage
aromatics from benzene to C10+ aromatics. The performance crystallisation step.
final product distribution depends on naphtha The hybrid configuration is suitable for exist-
composition and cut points. ing crystallisation-based complexes to be
revamped: the implementation of a hybrid Eluxyl
Reforming step allows at least a doubling of the capacity of
This high-severity, continuous-catalyst-regenera- an existing crystallisation plant.
tion (CCR) reforming process produces aromatics The process for separating high purity PX from
and hydrogen, an important, if not the only, a C8 aromatics mixture uses the concept of simu-
source in the complex. To maximise aromatics lated countercurrent adsorption. Eluxyl was

2 PTQ Q2 2004 www.digitalrefining.com/article/1000279

designed to expand single train capacity limits The multiple on/off valve system managed by
using advanced concepts that allow flexibility programmable logic controllers (PLC) brings a
and near-ideal hydraulic control. The proven high degree of flexibility and allows a continu-
ability to reach single train capacities as high as ously optimised operation. The on/off valve
750000 tons/year enables the operator to bring concept simply neutralises any limitations in
economy-of-scale advantages to each unit in the liquid volume handling: larger capacities simply
complex. mean larger valve diameters. Valves are available
High, single-train capacities raise a number of from several qualified vendors. Qualification test
developmental challenges in the scale-up of is equivalent to more than six years operation
liquid-full adsorption sections. These issues were without failure or leaks. Industrial experience
addressed during the early stages of develop- demonstrates the reliability and flexibility of this
ment and have inspired some of the technology technology. Valves can be taken off line for
features. These features are now completely maintenance or replaced with no interruption in
industrially proven, including: service.
• Adsorbent characteristics Another feature of the PLC system is its ability
• Adsorber loading to be tuned to accommodate the very character-
• Efficient distribution-withdrawal trays istics of the unit. For example, the pumparound
• Multiple on/off valve system managed by lines that convey the concentration profiles from
programmable logic controllers (PLC) one adsorber to the other are considered to be
• Management of non-selective volume non-selective volumes; the larger the production
• Online Raman spectroscopic analysis. capacity, the larger is their volume relative to the
Adsorbent characteristics are all-important adsorption beds. The PLC system can compen-
keys to achieving the highest PX purity and sate for this deviation from the ideal. This
recovery rates. The constraints peculiar to simu- proprietary management of non-selective volume
lated moving bed technology require the feature ensures maximum use of the loaded
adsorbent to have an adequate balance between molecular sieve.
selective pore volume and mechanical strength. In addition to providing economy-of-scale
Adsorber loading procedure and control of benefits to the operator, the Eluxyl investment
particle size distribution are most important requirement is intrinsically lower since the cost
parameters in obtaining homogeneous particle of the single source proprietary items is reduced.
distribution in the bed and achieve a near-perfect Online Raman spectroscopic analysis is applied
plug-flow pattern throughout the adsorption to visualise real time concentration profiles in
section. The proprietary Catapac system is widely the adsorption columns. This powerful technique
used in the industry for dense and homogeneous allows highly tuned and continuous supervision
catalyst and adsorbent loading operations. The of the adsorption process.
combination of an efficient loading technique Since 1995, eight Eluxyl licences have been
and the narrow size distribution of the particles awarded for a total paraxylene production capac-
enable homogeneous sieve particle distributions ity of over 2.9 million tons/year. Capacities for
to be achieved in adsorbers having diameters up these units range from 180000 to 750000 tons/
to 8m. year, all of them in single-train.
Efficient distribution-withdrawal trays are key
features of the technology. Targeting large, Isomerisation to PX
single-train capacities requires even distribution The Eluxyl raffinate stream contains ethyl
of entering feed and withdrawal of product benzene (EB), orthoxylene and metaxylene.
throughout the bed sections in large diameter Depending on market objectives, they can
adsorbers. Blending efficiency and injection undergo an isomerisation step that establishes a
synchronisation issues are properly addressed new equilibrium mixture of these components
and industrially proven. Large adsorption and PX. The isomerisation unit effluent is recy-
sections also require adequate mechanical resist- cled via the xylenes distillation column to the
ance for the distribution/withdrawal trays; these Eluxyl unit where PX is recovered and purified.
aspects are also included in the design of the The proprietary XyMax technology for EB
internals.

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 Petroleum Corporation (CPC) of
100 Taiwan. The first industrial unit was
put on stream in June 1997 in CPC’s
80 petrochemical plant in Lin-Yuan where
Xylenes loop
60 Disproportionation/ an existing transalkylation unit was
transalkylation retrofitted with the TransPlus process.
%

40 Arom extraction This technology builds on experience

Full range naphtha in toluene disproportionation that
20 to aromatics
began in the mid-1970s. TransPlus is
0
now in operation in two units and two
CAPEX OPEX grassroots applications are under
completion at design or erection stage.
Figure 3 Building blocks Capex and Opex contributions The process utilises a proprietary
catalyst that has superior yield
dealkylation and xylene isomerisation is a new performance. This is achieved with a careful
generation technology that further increases EB catalyst design that maximises desirable reac-
conversion and reduces xylene losses. tions such as disproportionation, transalkylation
At present, there are 17 units using this isom- and dealkylation and minimises undesirable side
erisation technology. Some of the technology’s reactions. The process has the ability to process
features include a high space velocity that results heavy feedstocks: any aromatic boiling below
in smaller reactor and volume requirements and naphthalene can be converted to valuable
therefore lower investment cost. In addition, benzene and C8+, thus increasing the overall
reduced H2/HC requirement results in further yields.
savings in investment and operating costs while In addition, this process has the advantage of
achieving long cycle lengths owing to the excep- low capital and operating costs due to more
tional stability of the catalytic system. favourable operating conditions relative to
When the objective is to place more emphasis competitors’ processes, which result from the
on the isomerisation of ethyl benzene than on its more robust nature of the catalyst.
dealkylation, a different catalyst-based technology Low H2/HC mole ratio and higher weight
can be used. For example, the proprietary Oparis hourly space velocity also characterise TransPlus
catalyst developed by IFP for EB and xylenes technology and make it possible for grassroots
isomerisation, effectively converts EB into addi- plants to have lower capital and operating costs
tional xylenes. A breakthrough in overall relative to competing technology. Higher catalyst
performance was achieved owing to an optimal activity and a lower hydrogen recycle require-
balance between catalyst activity and selectivity. ment characterise intrinsically stable catalysts.
Higher catalyst activity leads to lower reactor This enhances the plant stream factor, which is
volume and thereby lower investment for the another way to maximise investment return.
isomerisation section. Oparis catalysts were
successfully commercialised in early 2001 as a Benzene and toluene recovery
drop-in replacement in a recently commissioned The proprietary Morphylane process, developed
plant designed by others. Oparis catalysts have by Uhde-Edeleanu, extracts aromatics from other
successfully been regenerated in situ, with no close-boiling hydrocarbons. This extractive distil-
loss in activity or selectivity. A second load of the lation process employs the concept that a solvent
catalyst began service in November 2002 by the can be used to modify the relative vapour pres-
same owner at another plant site. Two more sures of aromatics in a cut in such a way that
units are due to switch to Oparis in the first half they can be separated from non-aromatics by
of this year. simple distillation.
Some of the characteristics of the process
Transalkylation of toluene/C9+ observed at over 40 locations where the units
The proprietary TransPlus technology is have been licensed:
ExxonMobil’s toluene/C9+ aromatics transalkyla- • The Morphylane process features a compact
tion technology, co-developed with the Chinese and cost-effective design, reducing the number

4 PTQ Q2 2004 www.digitalrefining.com/article/1000279

of equipment items compared to conventional Option 1 summary
liquid-liquid extraction technologies
• Cost effective recovery and high purity aromat-
Oparis XyMax
ics is achieved owing to a carefully selected option option
solvent: NFM is a non-corrosive material, ther- Total reformate, 000 tpa 1400 925
mally and chemically stable; no other chemical C8A in reformate, 000 tpa 432 152
needs to be injected in the process, which Mixed C8 aromatics
import, 000 tpa – 340
contributes to the ease of operation Paraxylene, 000 tpa 400 400
• Divided wall column technology has recently Crude benzene, 000 tpa – 60
been applied to the extractive distillation Reformate C8A fraction
concept, providing for further reduction of to PX block, % ~100 ~55
RON penalty -3.8 -1.8
investment and operating costs. MON penalty -2.6 -1.4
Figure 3 summarises typical relative invest-
ment and operating cost contributions of the
major process unit building blocks in a world- Table 1
scale complex producing 600000 tonnes/year
PX, 100000 tonnes orthoxylene (OX) and reformate and mixed xylenes using EB dealkyla-
295000 tonnes benzene (BZ). A full range naph- tion type isomerisation technology (XyMax).
tha feed of 1.3 million tpa is consumed. The XyMax option has benefits in terms of
Figure 3 underscores the weight attributed to both capital expenditure (Capex) and operating
generating the aromatics “backbone” in the over- expense (Opex), but downstream processing of
all complex, highlighting the interest for future crude benzene needs to be taken into considera-
producers, either to find opportunities to produce tion. Overall, PX yield is also lower since EB
BTX from existing aromatic resources, or to does not participate in PX production. On the
combine their aromatic intermediate production other hand, the Oparis option yields more PX
objectives with a gasoline blend stream. The from an equivalent amount of C8 aromatics but
latter option will provide some operational flexi- at the cost of higher Capex and Opex, resulting
bility to swing production from BTX from thermodynamic limitations in the conver-
intermediates to gasoline blend depending on sion of EB to xylenes, thus to higher xylene loop
market demand. hydraulics.
The impact on the residual reformate charac-
Option 1 teristics is shown in Table 1 and indicates a
Using existing resources rather linear relationship between the fraction of
Aromatics are significant gasoline pool constitu- C8 aromatics cut withdrawn from the reformate
ents. New gasoline specifications limiting the and octane penalty. Either of these technologies
total aromatics content in the gasoline pool are
to take effect in western Europe in 2005, eventu-
ally expanding eastwards to the Indian C7– cut to
gasoline
subcontinent and Asia.
The European market for gasoline is stagnant,
Eluxyl PX
if not slightly decreasing, the main reasons being
the ever-increasing competition from the diesel
engine and government tax incentives. As a High sev.
result, refiners may look at petrochemical value reformate C8A
BT cut to
for excess aromatics in their gasoline pool. isom.
gasoline
Figure 4 displays a solution for “valorisation”
of C8 aromatics, mainly into PX.
Two case-studies are displayed in Table 1:
Case 1 C8 aromatics from reformate are used to C9+ to
C8+ gasoline
yield paraxylene, applying mainly EB and xylenes
isomerisation technology (Oparis)
Case 2 PX and crude benzene are produced from Figure 4 Reformate-to-PX route

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 Option 2 summary contains important fractions of aromatics.
In a gasoline blending formula, the HPG value
is often offset by the associated requirement for
Option 2 Excess reformate
and HPG feeds, 000 tpa
diluting its aromatics back to the 35 vol% objec-
Captive HPG 327 tive. In this respect, HPG can be a good
Imported HPG 87 candidate to feed a BTX production facility
Light reformate 493 (Table 2) as long as the following prerequisites
Heavy reformate 238
Paraxylene 500
are met:
Benzene 221 • Adequate HPG treatment: the removal of
unsaturated hydrocarbons and sulphur
Table 2 compounds is essential prior to aromatics recov-
ery; this requires broad experience in designing
enables an operator to maximise aromatics plants offering adequate levels of reliability, even
production from a given C8 aromatics feedstock when partially hydrotreated feedstock is
and minimum investment. imported
• Extraction of aromatics is necessary as soon as
Option 2 HPG becomes a major source to the complex;
Using reformate and pyrolysis gasoline HPG non-aromatics are essentially naphthenic in
Hydrotreated pyrolysis gasoline represents an nature, and these compounds are more difficult to
important source of aromatics and its availabil- crack on advanced zeolite catalysts – Sulfolane
ity depends on the feedstock used to produce liquid-liquid extraction for BTX and C9+ then
ethylene and propylene. Naphtha crackers typi- becomes the preferred technology
cally yield 20–30% pyrolysis gasoline. • HPG C8 aromatics contain large amounts of
Hydrotreated heavy pyrolysis gasoline EB compared to the C8 aromatics in reformate.
(HPG) has a significant octane value, but also The application of TransPlus technology to yield
maximised amounts of low EB content
Raffinate
C8 aromatics, allows dilution of EB to
equal average reformate C8 aromatics
Benzene
concentrations. In this scheme, the use
of Oparis in the Xylenes loop ensures
Tol. effective and selective isomerisation of
Light reformate
BTX C8 aromatics.
ext. Figure 5 displays a proposed configu-
Captive ration to produce BTX from excess
HPG reformate and hydrotreated pygas.
The performance offered in this plant
Pygas
HDT configuration results mainly from
TransPlus performance allowing
HPG HPG C10+
import processing of most of the heavier
Paraxylene
aromatics from the heavy reformate
stream to yield EB–lean C8 aromatics,
thereby diluting the EB contained in the
Xylenes loop Tol–A9–A10 HPG C8 aromatics cut.
To FO • Oparis Transalkylation
• Eluxyl TransPlus
Option 3
C9+ BTX Production and octane blending
C9+ reformate
With growing environmental concerns,
Asian countries may soon have to
C11+ comply with stringent gasoline quality
aromatics
requirements. In these countries,
however, the demand for gasoline is still
Figure 5 HPG and excess reformate configuration expanding, and there are incentives for

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 Option 3 summary
Gasoline blend
Benzene
BTX and gasoline blend
from naphtha and HPG,
000 tpa
Heavy naphtha 800
Hydrotreated HPG 406 Extraction Toluene
Paraxylene 450
Hydrotreated HPG
Benzene 159
C7–
Gasoline blend 375
Gasoline Blend
RON/MON clear 105/94 Naphtha NHDT and
aromising

Table 3

new complexes to move towards refin- Paraxylene

ery-petrochemical integration, which
will enable them to process a wide Tol–A9–A10
Xylenes loop Transalkylation
range of feedstocks to yield benzene, • Oparis/XyMax TransPlus
paraxylene and octane blend streams. • Eluxyl
Figure 6 displays this type of plant C9 & C10
configuration. C 9 +
In the Option 3 configuration, the
hydrotreated HPG contribution (Table Heavy
3) and component distribution are aromatics
such that only the BT cut needs to be
Gasoline blend
extracted in the Morphylane extractive
distillation unit. This allows a further
reduction in capital and operating Figure 6 Produce BTX and gasoline blend from naphtha and HPG
costs associated with the separation of
high purity benzene and toluene from the creation in 2001 where he assumed his current position. He holds
combined light reformate and hydrotreated HPG an engineering degree from the Institut de Chimie et Physique
BT fraction. Industrielles de Lyon and a post-graduate degree in refining and
In conclusion, the benefits of refining and petro- petrochemicals from the IFP School.
chemical integration stand out either as an add-on E-mail: [email protected]
facility to a refinery environment, or a grassroots Françoise Montecot is senior technical manager for gasoline and
integration including cracker and gasoline produc- petrochemicals in Axens’ marketing and technology department
tion. Each integration project is site-specific and at Paris, Texas, USA, and is responsible for technical proposals
requires customised study to maximise benefits in aromatics, oligomerisation and cyclohexane processes. While
with IFP she became proposal engineer for hydrogenation,
from existing resources and to meet production
oligomerisation, MTBE and cyclohexane processes in the
objectives within defined constraints. IFP industrial division, joining Axens in 2001. She holds an
engineering degree from Ecole Polytechnique Féminine.
Jacques Rault is product line manager for aromatics technologies E-mail: franç[email protected]
in Axens marketing and technology department in Paris. Before
the creation of Axens in 2001, he was technology manager in IFP’s
industrial division, in charge of aromatics technology applications.
Links
He holds a bachelor’s degree in process engineering from Ecole
More articles from: Axens
Centrale de Lille and a masters in applied chemical engineering
from the IFP School. E-mail: [email protected] More articles from the following categories:
Christian Dupraz is director of the marketing and technology Alkylation Catalysts & Additives
department for gasoline and petrochemicals at Axens. While in Design, Engineering & Construction
the industrial division of IFP he held various positions, including Gas Processing/Treatment Hydroprocessing
process engineer, sales and marketing manager for the Far East, Isomerisation Petrochemicals Reforming
and finally proposal department director. He joined Axens at its

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