Squeezing the Most out of BTX Investments

Authors: J. Rault, F. Montecot, C. Dupraz

Axens
89, bd Franklin Roosevelt
BP 50802
92508 Rueil Malmaison Cedex, France
www.axens.net

Introduction
With an expected annual demand growth rate of 6% to 8% for the next decade,
paraxylene (PX) is a healthy market. Recent overcapacity situation, combined with
Asian economic turmoil has severely impacted the PX industry profitability and
recovery is likely to relieve pressure on producers later than sooner. According to
multiclient reports, PX demand should catch with existing or scheduled capacity by
the year 2004, and new prospects for grassroots projects emerge. Future PX
producers seek solutions to maximize their investment return, and maintain
profitability during the low side of the intermediates market cycle.
This paper outlines how Axens ParamaXTM portfolio of technologies for aromatics
production can increase plant competitiveness through various angles, such as
lowering initial investment and operating costs, stream factor enhancement, and
overall plant selectivity.
ParamaX - The BTX Aromatics Technology Suite
The processes incorporated in this portfolio provide customers with a complete suite
of advanced technologies. Together, they make an attractive first choice when
selecting the full set of BTX technologies and services from a single source. The
technologies exclusively licensed by Axens in grassroots ParamaX packages are:
Aromizing - high severity CCR reforming for aromatics production,
Arofining - reformate olefins saturation for drastically reduced clay
consumption,
Sulfolane (Lyondell) - high purity benzene, toluene and xylenes extraction,
Morphylane (Uhde) - toluene and high purity benzene extraction,
Eluxyl - simulated countercurrent adsorption PX separation,
Crystallization - production of ultra-high purity PX when combined with
Eluxyl in the hybrid version,
Oparis - new generation xylenes and ethylbenzene (EB) isomerization,
XyMaxSM (ExxonMobil) - xylenes isomerization with EB dealkylation, using
the newly commercialized EM-4500 catalyst with improved activity and
selectivity,
PxMaxSM (ExxonMobil) - state-of-the-art Selective Toluene DisProportionation
(STDP) technology for the production of a highly PX-enriched xylene stream
and benzene,
TransPlusSM (ExxonMobil) - toluene/C9+C10 aromatics transalkylation, with
the proven ability to process high amounts of C9 and C10 aromatics,
MTDP-3 (ExxonMobil) - toluene disproportionation to benzene and xylenes.

Typical PX Production Complex (Figure 1)

A naphtha heart cut is first hydrotreated to remove sulfur and nitrogen prior to
feeding the Aromizing unit yielding a full slate of aromatics compounds and
hydrogen. Considerably more hydrogen is produced than consumed in the complex,
making it a net exporter.
The Arofining reactor, located upstream of the Aromizing effluent stabilization,
hydrogenates undesirable olefins and diolefins present in the high severity
reformate. This unit significantly prolongs clay lifetime (not shown in the figure),
resulting in lower costs associated with clay purchase and change-out.
The effluent is then split into C7- and C8+ fractions.

Raffinate
Benzene
H2

Naphtha
Hydrotreater

C7-

Toluene

Extraction:
- Morphylane
- Sulfolane

Tol-A9-A10
Transalkylation
TransPlus

Aromizing
& Arofining

Paraxylene
C8+

PX
Separation
Eluxyl

Naphtha

C8

C8A Isom.

- Oparis
C8+
- XyMax

C9+C10

C9+

Heavy
Aromatics

Figure 1 -Typical Aromatics Complex

Non-aromatic compounds are removed from the C7- fraction with Morphylane
extractive distillation unit or in a Sulfolane liquid-liquid extraction process. The latter
is preferred when very high purity toluene production is envisaged or when an
external feed, such as hydrotreated pygas, is destined to go through BTX extraction.
Morphylane is ideally used when toluene is internally transalkylated.
Xylenes Loop: the C7/C8 splitter bottoms are sent to the xylenes rerun column,
together with the C8+ effluent from the TransPlus unit and the recycle from the
isomerization unit. The C8 fraction, taken overhead, feeds the Eluxyl unit, which
produces high purity PX from the mixed C8 stream at high recovery rates. The PXdepleted stream then feeds the isomerization section for which EB-reforming type
(Oparis) or EB dealkylating type (XyMax) technologies may be selected. The effluent
from the isomerization process, a close to equilibrium mixture of xylenes, is then

recycled to the xylenes rerun and Eluxyl. The selection of isomerization technology
is a function of the desired BTX production pattern and economical concerns.
The xylenes rerun bottoms are sent to a heavy aromatics splitter where C9 and C10
aromatics are taken overhead as feed to the TransPlus.

Economy of Scale: Lower Relative Investment

Ultimate single train capacities:
Tomorrows PX producers will have to meet the requirements of the downstream
industry. Recent technical improvements in PTA manufacturing technology now
allow the building of grassroots capacity consuming 500,000 tons per annum (TPA)
or more PX, and the economy of scale realized owing to these developments needs
to be matched with future Aromatics complexes. Axens technology offerings are
designed to meet this challenging scenario.
Aromizing technology is a high severity reforming process for aromatics
production from naphtha feedstock. To maximize aromatic production, high
temperature and low pressure operation is achieved using a specific high selectivity
catalyst (AR 501) and the well-known Axens continuous catalyst regeneration
technology. From the hydrocarbon standpoint, Aromizing technology is similar in
layout as a conventional fixed bed reformer. The continuous catalyst circulation is
ensured by a series of lift lines that convey catalyst beads from the bottom of one
reactor to the top of the next reactor (see Figure 2).

Regenerator
Reactors
and Heaters

H2 rich gas
Booster
Compressor

Recovery
System

Feed
Recycle
Compressor

To
Stabilization

Figure 2 - Simplified Aromizing Flowscheme

This sound side-by-side reactors arrangement results in simple reactor design, low
profile structure, easy and low-cost engineering and construction. More practically,
Aromizing reactors thickness results from their process service without mechanical

or thermal expansion constraints. Based on this side-by-side arrangement, reaction

heaters are logically located in front of each reactor, resulting in short transfer lines,
and reduced mechanical and thermal constraints. This leads to a compact and low
cost technology.
The catalyst circulation and regeneration system, resulting from more than 30 years
of industrial experience, is fully automated and ensures very low catalyst
consumption by attrition as well as stable performance during catalyst life.
Eluxyl achieves the separation of high purity PX from a C8 aromatics mixture with
high recovery per pass, using the concept of simulated countercurrent adsorption.
Eluxyl was designed to displace the limits of single train capacities owing to
advanced concepts that allow flexibility and ideal hydraulics management. This
proven ability to reach single train capacities as high as 700,000 TPA allows
benefiting from economy of scale on all the building blocks of the complex.
High single train capacity raises a number of development issues in the scale-up of
liquid-full adsorption sections. These issues have been taken into account at the
early stages of Eluxyl development and have driven some of the technology options.
All these options are now completely industrially proven.
Adsorbent characteristics are an important key to reach ultimate PX purity
and high recovery rates, and because of the constraints of Simulated Moving
Bed technology, the adsorbent needs to have the adequate balance between
selective pore volume and mechanical strength.
Adsorber loading procedure and particle size distribution is another
important parameter to monitor to ensure even bed density distribution and
achieve piston flow pattern through the adsorption section. Axens CatapacTM
system is widely used in the industry for catalyst dense loading operations.
Catapac concept was adapted for molecular sieve loading. The combination
of this efficient dense loading apparatus and a narrow particle size distribution
enables to reach even bed density distribution, in adsorbers as large as 7 to 8
meters diameter.
Efficient distribution/withdrawal trays are another key feature of Eluxyl
technology. Targeting large single-train capacities requires even distribution
of feeds and withdrawal of products in wide diameter adsorbers. Blending
efficiency, and injection synchronicity issues are properly addressed and
industrially proven. Large adsorption section also require an adequate
mechanical resistance for the distribution/withdrawal trays: these aspects are
also included in the design of the internals.
The PLC controlled on/off valves system clearly distinguishes Eluxyl
technology, bringing a high degree of flexibility and a continuously optimized
operation. The on/off valves allow to turnaround any limitation in liquid
volumes handling: larger capacity simply means larger valves size.
Non selective volume management. Another feature of the PLC system is
its ability to be tuned to incorporate some physical characteristics of the unit:
the pumparound lines that convey the concentration profile from one adsorber
to the other are a non selective volume and the larger the capacity, the larger
their volume relative to adsorption beds. The PLC system allows
compensating for this deviation to ideality. This proprietary feature ensures a
maximized use of the loaded molecular sieve.

Eluxyl technology allows benefiting from economy of scale but is also intrinsically
lower in investment since the number of single source proprietary items is reduced.

Lower Initial Investment

The technologies offered in the ParamaX portfolio apply concepts or use catalytic or
solvent systems that drive the investment downwards, owing to reduced number of
equipment for a given process service, or smaller equipment size compared to
alternate technologies.
Morphylane has imposed itself as the industry standard for the extraction of a
narrow boiling range aromatics cuts. It employs the concept of extractive distillation
where a solvent is used to modify the relative vapor pressures of various
hydrocarbons in such a way that aromatics can be separated from non-aromatics by
simple distillation.
Compact and cost-effective design is the key characteristic of Morphylane
that uses a reduced number of equipment compared to conventional
liquid-liquid extraction technologies.
Cost effective recovery and high purity aromatics is achieved owing to a
carefully selected solvent: NFM is a non-corrosive material, thermally and
chemically stable. No other chemical needs to be injected in the process
which contributes to the ease of operation.
Divided wall technology has recently been applied to the Extractive
distillation concept, providing for further reduction of investment and
operating costs.
Today, more than forty Morphylane units have been licensed worldwide.
XyMax technology for EB dealkylation type xylene isomerization is exclusively
available through the ParamaX alliance for grassroots applications. ExxonMobil
Chemical Company earlier generation MHAI and Advanced MHAI technologies have
a well established reputation worldwide. XyMax is a new generation technology
resulting from Exxon Mobil Chemical Company efforts to further increase EB
conversion and reduce xylene loses. XyMax features a level of performance that will
re-enforce the existing strong worldwide market position in xylenes isomerization. At
present there are 17 units using ExxonMobil xylenes isomerization technology, and
over one-third of the worlds xylenes isomerization capacity uses ExxonMobil
catalysts. The first batch of XyMax catalyst was put on stream in April 2001 in
Singapore. Since its commercialization, two more units have switched to XyMax
catalyst.
High space velocity is one of the trademarks of ExxonMobil technologies,
and XyMax maintains the high space velocity standard. This results in small
reactor volume requirement and therefore lower investment cost;
Reduced H2/HC requirement results in further savings in investment and
operating costs, while achieving long cycle lengths owing to the exceptional
stability of the catalytic system.
Oparis is a new generation catalyst developed by IFP for EB and xylenes
isomerization. It effectively converts EB into additional xylenes.

Breakthrough overall performance is achieved owing to an optimal balance between

catalyst activity and selectivity. Higher catalyst activity leads to lower reactor volume
and thereby lower investment for the Oparis section.
Oparis was successfully commercialized in early 2001 as a drop-in replacement in a
recently commissioned plant designed by others. A second load of Oparis catalyst
was serviced in November 2002, to the same user, on another jobsite.
TransPlus technology for toluene/C9+ aromatics transalkylation, co-developed by
ExxonMobil and the Chinese Petroleum Corporation (CPC) of Taiwan, is also
exclusively available through the ParamaX Alliance for grassroots applications. The
first industrial unit was put on stream in June 1997 in CPCs petrochemical plant in
Lin-Yuan where an existing transalkylation unit was retrofitted with the TransPlus
process. This technology builds on ExxonMobil's extensive experience in toluene
disproportionation that began in the mid-1970s.
The TransPlus process utilizes a proprietary catalyst that has superior yield
performance. This is achieved with a careful catalyst design that maximizes
desirable reactions such as disproportionation, transalkylation and dealkylation and
minimizes undesirable side reactions. In addition, TransPlus has the advantage of
more favorable processing conditions compared to other processes: low H2/HC mole
ratio and high space velocity characterize TransPlus technology and make it
possible to build grassroots plants at lower capital costs. This also results in reduced
operating cost while maintaining long cycle lengths.
Higher catalysts activity and lower hydrogen recycle requirement characterize
intrinsically stable catalysts. This allows enhancing the plants stream factor, which is
another way to maximize the investment return.

Enhance Plant Stream Factor

When it comes to yearly profit evaluation, plant stream factor turns out to be an
important figure, and when evaluating technologies, one should take into account
the frequency of catalyst regeneration or replacement, as these operations are on
the critical path during maintenance turnaround.
Aromizing regeneration system is designed to perform smooth and efficient
catalyst regeneration where the catalyst support structure is left undamaged.
As a result, typical catalyst life in Axens Aromizing technology can be as long
as nine years, with an average of six years.
Eluxyl technology uses on/off valves available from qualified manufacturers.
The PLC system that monitors the valves enables to perform preventive
valves maintenance while keeping the unit in operation and products on
specifications.

XyMax, in the continuity of former generation MHAI and Advanced MHAI

technologies, features a low catalyst aging rate. Cycle length as long as 10
years can reasonably be expected, as indicate the current aging trends
measured on the first XyMax industrial application.
Oparis features a significantly improved aging pattern compared to previous
generation catalysts. Oparis first application has already exceeded two years
in its first cycle.
TransPlus catalyst has achieved a six years first cycle in a retrofit application.
This first cycle had to be ended because of limitations on the initial unit design.

Morphylane technology uses a non corrosive solvent in an extractive

distillation concept. Turnaround inspection of a Morphylane unit is similar to
that of a conventional distillation system

Each complex building block proposed by Axens offers longer catalyst life or cycle,
resulting in shorter turnaround inspection or maintenance periods. They also offer
higher selectivity towards valuable final products.

Overall Selectivity Improvement

Overall selectivity to final products is the most effective way to increase plant
profitability and this can be achieved either by implementing higher selectivity
catalysts or by catalysts able to process a wider range of feeds compositions.
Aromizing technology sources aromatics for the whole downstream plant.
Axens has recently commercialized AR-501, a new generation catalyst,
dedicated to aromatics production. This catalyst is in operation in three units
so far, one of them in a non-Axens technology. Owing to the quality and
smoothness of the continuous regeneration system, Aromizing technology
ensures high aromatics yield that are maintained all through the life of the
catalyst.
XyMax technology offers an unmatched level of selectivity: even at high EB
conversions xylenes losses per pass are extremely low, leading to a PX to
xylene ration in the range of 97 % for the xylene loop.
Oparis, when implemented in the xylenes loop, boosts overall performance up
to 93% PX out of C8 aromatics feedstock.
TransPlus technology has the flexibility to process up to 100 wt % of C9+
aromatics in the fresh feed while maintaining long cycle lengths. In addition,
the robust nature of the TransPlus catalyst allows extensive recycle of the
C10/C11 aromatics in the C9+ feedstock enhancing the yields towards xylenes
production as illustrated in Figure 3. TransPlus therefore enables to convert
most of the heavy aromatics produced in the Aromizing into additional
benzene and xylenes to feed the xylenes loop, and enhance the overall
aromatics yield of the plant.

80
75
Xylene Yields
on
Fresh Feed,
wt%

/ C 10
/C 9
ene
u
l
To

70

d
Fee

65
C9 F
ene/
Tolu

60

eed

55

50
0

10

20

30

40

50

60

70

80

90

100

C9+ Aromatics in Fresh Feed, wt%

Figure 3 - Improved Xylene Yields via Transalkylation of C9/C10 Aromatics

Conclusion
Axens ParamaX contains a complete set of technologies available from a single
source licensor which can be configured to meet all BTX production needs, with
reduced investment and operating costs, enhanced product yields that will be
maintained all through the cycle or life of the catalysts. The ParamaX Alliance
partners are committed to servicing the industry with continuously upgraded
technologies. Since the advent of the ParamaX Alliance, five major technology
advances have been integrated into the portfolio: Morphylane extractive distillation,
AR 501 CCR catalyst, XyMax technology, Oparis and PxMax.