Christian Dupraz and Jacques Rault – Axens, IFP Group Technologies

Fabio Alario - Kinetics and Catalysis Division, IFP

Scott Ramsey – ExxonMobil Chemical Company

MAXIMIZING PARAXYLENE PRODUCTION WITH PARAMAX

Introduction
With an expected annual demand growth rate of 6% to 8% for the next decade,
Paraxylene can be described as a healthy market. In spite of the recent overcapacity
situation, industry consultants tell us that demand for paraxylene is expected to
catch up with production capacity by the end of 2003. This will require increased
production capacity, the lion’s share coming from new, world-scale grassroots units.
Today, the ParamaX suite of technologies offered by Axens addresses tomorrows
challenges: high capacity, flexibility and performance.

ParamaX - The BTX Aromatics Technology Suite The processes incorporated

into Axens aromatics portfolio provides customers with a complete suite of advanced
technologies, unmatched in performance and cost effectiveness for all BTX produc-
tion goals. Together, they make an attractive first choice when selecting the full
complement of BTX technologies and services from a single source. The technolo-
gies exclusively licensed by Axens in grassroots ParamaX packages are:
• Aromizing – high severity CCR reforming for aromatics production,
• Arofining - reformate saturation for drastically reduced clay consumption,
• Sulfolane (Lyondell) – high purity benzene, toluene and xylenes extraction,
• Morphylane (Krupp Uhde) – toluene and high purity benzene extraction,
• Eluxyl - simulated countercurrent adsorption paraxylene separation,
• Crystallization – enables the production of ultra-high purity paraxylene when
combined with Eluxyl in the hybrid version,
• Oparis™ – New generation C8 aromatics (xylenes and ethylbenzene) isomeriza-
tion,
• XyMaxsm (ExxonMobil) – xylenes isomerization with ethylbenzene dealkylation,
using the newly commercialized EM-4500 catalyst with improved activity and se-
lectivity,
• PxMaxsm (ExxonMobil) - state-of-the-art Selective Toluene DisProportionation
(STDP) technology for the production of a highly paraxylene-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, and
• MTDP-3 (ExxonMobil) – toluene disproportionation to benzene and xylenes.
Axens Maximizing Paraxylene Production with ParamaX

Typical Paraxylene Production Complex (Figure 1) A naphtha heart cut is first

hydrotreated to remove sulfur and nitrogen prior to feeding an Aromizing unit yield-
ing 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, hy-
drogenates undesirable olefin and diolefin compounds present in the high severity
reformate. This unit significantly prolongs clay (not shown) lifetime, resulting in lower
costs associated with: clay purchase and disposal, reactor loading and unloading
operations and reduced bed size. The effluent is then split into C7- and C8+ frac-
tions.

Figure 1 Typical Aromatics complex

Raffinate
Benzene
Extraction: Toluene
- Morphylane
H2
C 7- - Sulfolane

Tol-A9-A10
Transalkylation
Naphtha Aromizing TransPlus
Hydrotreater & Arofining
Paraxylene
PX C8A Isom. C8
C 8+ Separation C8-+Oparis
Eluxyl - XyMax C9+C10
Naphtha

C 9+
Heavy
Aromatics

Non-aromatic compounds are removed from the C7- fraction either in a 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 ex-
ternal feed, such as hydrotreated pygas, is destined to go through BTX extraction.
Morphylane is ideally used when toluene is internally transalkylated.
The deheptanizer bottoms sm are sent to the xylenes rerun column, together with the
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 paraxy-
lene from the mixed C8 stream at high recovery rates. The paraxylene-depleted
stream then feeds the isomerization section for which EB-reforming type (Oparis) or
EB dealkylating type (XyMaxsm) 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 column where C9 and C10
aromatics are taken overhead for the TransPlus feed. TransPlus affords a significant
increase in paraxylene production capacity by disproportionation / transalkylation of
toluene and C9+ aromatics, yielding additional mixed xylenes and benzene.

2
Axens Maximizing Paraxylene Production with ParamaX

Future directions for PX production plant configurations

Ultimate single train capacities:
Tomorrow’s Paraxylene producers will have to meet the requirements of the down-
stream industry. Recent technical improvements in PTA manufacturing technology
now allow the building of grassroots capacity consuming 500 kTA PX or more, 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, owing to its sound side-by-side reactors arrangement al-
lows high capacities without hitting any technical constraint from mechanical or
operational point of views,
- Eluxyl technology was designed to displace the limits of single train capacities
owing to advanced concepts that allow flexibility and ideal hydraulics manage-
ment,
- Axens is also offering breakthrough performance for the surrounding catalytic
systems that are used to rearrange the aromatic backbone (Transalkylation, Iso-
merization),
The ParamaX suite provides the best overall answer in both respect of economy of
scale and overall performance.
Refinery petrochemicals integration at large
New constraints on Gasoline formulation limiting the total amount of aromatics shall
be effective in Western Europe by 2005. These specifications will expand eastwards
to the Middle-East, Indian Subcontinent and Asia in the near future. These new
regulations, when combined with declining overall gasoline pool (such as in Western
Europe), or emerging countries that will aim at high standard mogas specifications,
will put refiners under pressure to properly manage their aromatics volumes. At the
other end of the scale, Naphtha cracking plants that have been exporting hydro-
treated Pyrolysis gasoline to the gasoline pool are also likely to face hard times to
sell out their aromatics rich co-product. The expected growth in Ethylene demand
will make this Pygas issue even more important in the future. Combining the existing
aromatics volumes in the refinery and crackers to set up a gasoline and aromatics
production facility is a solution that major operators are already looking into.
The flow schemes below give an illustration of alternate ParamaX configurations
corresponding to these new directions.
Figure 2 High Severity Reformate(s) to PX route

C7- cut to gasoline

Eluxyl PX

High Sev.
Reformate C8A
BT cut to Gasoline
Isom.

C8+
C9+ to gasoline

3
Axens Maximizing Paraxylene Production with ParamaX

The high severity reformate to PX route proposes to integrate PX production capac-

ity within a refinery environment, or as a common facility to several plants.

The Pygas and Reformate to PX route shows an overall integration between a

Naphtha Cracker plant and a Refinery.

Figure 3 Pygas and Reformate to PX route

Raffinate
Benzene

Extraction
Pygas Pygas HDT Toluene

Pygas C10+

C7 -
Paraxylene

Eluxyl Tol-A9-A10
Transalkylation
High TransPlus
C8A
Severity
Reformate
C8A isom C9 & C10
- Oparis
- XyMax

C9 +
Heavy
Aromatics

To serve the various configurations, Axens proposes the ParamaX suite of Tech-
nologies as a single source Licensor and service provider.
Features of Selected ParamaX Technologies
The following provides some the key features of selected ParamaX technologies.
Aromizing is Axens’ state-of-the-art CCR reforming technology for aromatics pro-
duction. The process employs the AR series of catalysts designed to maximize
aromatics yield and operates at low pressure and high severity.
Aromizing, represented in Figure 4, is a technically sound technology now backed-
up by extensive industrial experience and feedback.
• The continuous catalyst regeneration system is fully automated, controlling all
catalyst circulation and regeneration during start-up, shutdown and normal opera-
tions. The latest generation CCR system, RegenC, provides an independent control
of all the key parameters that ensure optimal catalyst regeneration resulting in
extended catalyst life and stable performance.
• AR-501 is the latest generation of Aromizing catalyst featuring an improved se-
lectivity towards aromatics owing to the uniform and ultra-high dispersion of active
metals on the carrier. A harder support material provides excellent mechanical re-
sistance and assures low catalyst consumption rates. The catalyst also features a
reduced platinum content, which has a direct impact on investment cost.
• The side-by-side reactor arrangement allows simple reactor design, implementa-
tion and maintenance access and easy handling of thermal expansion issues,

4
Axens Maximizing Paraxylene Production with ParamaX

resulting in cost-effective engineering and construction particularly when high ca-

pacities are considered.

Figure 4 Aromizing process flowscheme

Reactors and Heaters Regenerator

Booster
Compressor Hydrogen-Rich
Gas

Regen. Separator
Loop
Recovery
System

Feed Recycle Aromizate to

Compressor Stabilization

Aromizing technology is and will remain one of the key building blocks of future
Aromatics plant configurations.

Morphylane technology has imposed itself as the industry standard for the extrac-
tion 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
technology that uses a reduced number of pieces of equipment compared to
other 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.

Eluxyl process achieves the separation of high purity paraxylene from a mixture of
C8 aromatics based on the concept of simulated countercurrent adsorption.

Eluxyl incorporates a number of innovations from recent technological advances.

The concepts outlined hereafter have all been validated in the world’s largest oper-
ating single-train paraxylene separation unit, affirming its leading edge position.
• High performance adsorbent is the key to reach ultimate Paraxylene purity and
high recovery rates. The adsorption capability istm combined with adequate mechani-
cal strength, which allows use of the Catapac dense loading device: even bed
density is perfectly achieved, even on large adsorbers diameters.

5
Axens Maximizing Paraxylene Production with ParamaX

• Efficient distribution/withdrawal trays are another key feature of Eluxyl tech-

nology. Targeting ultra-large single-train capacities requires even distribution of
feeds and withdrawal of products in large diameter adsorbers. Blending efficiency,
and injection synchronicity issues are properly addressed and industrially proven.
• The PLC controlled on/off valves system clearly distinguishes this technology,
bringing a high degree of flexibility and a continuously optimized operation.
• On-stream maintenance of an individual valve during unit operation is achiev-
able owing to the ability of the microprocessor to automatically detect valve
malfunction. Maintenance is performed by plant maintenance personnel with lower
incurred costs, while maintaining unit performance.

• On-line Raman spectroscopic analysis is applied to visualize concentration

profiles along the Eluxyl adsorber on a real time basis. This powerful technique al-
lows a fine and continuous supervision of the adsorption section.
Eight Eluxyl licenses have been awarded so far, for a total paraxylene production
capacity of over 2.9 million metric tons per year and corresponding to 30% PX ca-
pacity share since this technology was brought to the market. The production
capacities range from 180,000 to 750,000 metric tons per year.
Today , the world’s largest single train capacity is based on Eluxyl technology and
serves the market with 650,000 tons per year of 99.9% paraxylene purity.
Oparis™ is a new generation catalyst for ethyl benzene (EB) and xylenes isomeri-
zation. Oparis™ effectively converts EB into additional xylenes.
Breakthrough performance is achieved in both terms of selectivity and activity.
When applied in a conventional Xylenes loop, Oparis™ yields up to 93% Paraxylene
out of C8 aromatics. This unmatched level of performance is achieved with a lesser
amount of catalyst compared to previous generation catalysts. Oparis™ is the pre-
ferred option whenever Benzene co-production needs to be minimized or eliminated.
It is also a valuable option whenever Pyrolysis gasoline C8 aromatics, that are
known to contain a lot of EB, are used as additional feed to the complex and Ben-
zene co-production is undesireable.
EB isomerization proceeds via a C8 naphthenic intermediate equilibrium that limits
the rate of reaction. Accurate management of the C8 naphthenes balance through
the reactor is therefore essential for optimizing process performance. With the im-
plementation of a dedicated C8 naphthenes recycle column, the Isomerization
section performance is finely optimized owing to an internal recirculation.
Oparis™ was successfully commercialized in early 2001 as a replacement for a
competitor’s catalyst in a recently commissioned plant.
ExxonMobil’s XyMaxsm technology for EB dealkylation type xylene isomerization is
exclusively available through the ParamaX Alliance for grassroot applications. The
earlier generation MHAI and Advanced MHAI technologies have a well established
reputation worldwide. ExxonMobil Chemical Company continues the push toward
higher ethylbenzene conversion, while further reducing xylene losses by bringing a
new generation catalyst to the market place: The EM-4500 catalyst features a level
of performance that will re-enforce the existing strong worldwide market position in
xylenes isomerization. At present there are 21 units using ExxonMobil xylenes iso-
merization technology, and over one-third of the world’s xylenes isomerization
capacity uses ExxonMobil catalysts. The first batch of EM-4500 catalyst was put on
stream in April 2001 in ExxonMobil's Jurong, Singapore plant.

6
Axens Maximizing Paraxylene Production with ParamaX

The process is distinguished by a unique dual-bed catalyst system. Ethylbenzene

dealkylation to benzene and non-aromatics cracking occur in the first bed, while the
near-equilibrium isomerization of xylenes takes place in the second bed.
XyMax using EM-4500 catalyst exhibits some key performance enhancements com-
pared to previous generation catalysts.
• Selectivity is further improved, and compared to Advanced MHAI, EM-4500 fea-
tures a further 50% reduction in xylenes losses. PX approach to equilibrium
remains in the range of 100%, and the selectivity of EB dealkylation to Benzene
has been improved.
• Higher EB conversion per pass is achieved without detrimental effect on the
catalyst cycle length. Based on the aging rate observed so far at the Jurong facil-
ity, EM-4500 is expected to exceed a five-year first cycle
• High space velocity is one of the trademarks of the ExxonMobil technologies,
and EM-4500 maintains the high space velocity standard.
• Reduced H2/HC requirement for EM-4500, resulting in further savings in invest-
ment and operating costs.

TransPlussm is ExxonMobil's toluene/C9+ aromatics transalkylation technology

which was co-developed with the Chinese Petroleum Corporation (CPC) of Taiwan.
The first industrial unit was put on stream in June 1997 in CPC’s 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-1970’s.
The TransPlus process utilizes a proprietary catalyst that has superior yield per-
formance. 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 low capital
and operating costs due to more favorable operating conditions relative to competi-
tor processes, which result from the more robust nature of the catalyst.
• Feedstock flexibility: 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 5.
Figure 5 Improved xylene yields via transalkylation of C9/C10 aromatics

80

75
d
F ee
C9/C 1
0
Xylene Yields e/
70 ue n
on T ol
Fresh Feed,
wt% 65
eed
/ C9 F
ene
60 T olu

55

50

0 10 20 30 40 50 60 70 80 90 100

C9+ Aromatics in Fresh Feed, wt%

7
Axens Maximizing Paraxylene Production with ParamaX

• Long cycle length: Typical performance of the fully regenerable TransPlus cata-
lyst shows that cycles in excess of several years can be expected even when
processing feedstocks having up to 100 wt% C9+ aromatics in the fresh feed.
• Benzene co-product purity is higher than 99.85 wt% purity thereby reducing the
need to re-process it through the extraction section.
• Low H2/HC mole ratio and higher weight hourly space velocity also charac-
terize TransPlus technology and make it possible to build grassroots plants at
lower capital costs relative to competitor technology. This also results in reduced
operating cost.
Considering the structure of present and future aromatics plants, TransPlus technol-
ogy is due to take a growing share of the C8 aromatics production to feed the
xylenes loop. TransPlus performance and versatility shall definitely be a key to com-
petitive plant operation.
PxMaxsm is ExxonMobil's State-of-the-Art technology for Selective Toluene DisPro-
portionation for the production of a highly paraxylene-enriched xylene stream and
benzene. The PxMax technology was first offered for licensing beginning in the fall
of 2000, and is the subject of a separate paper at this conference.

Conclusion
Axens’ ParamaX Technology Suite contains a complete set of technologies from a
single source which can be configured to meet all BTX production needs. The
ParamaX Alliance is committed to servicing the industry with continuously upgraded
technologies. Since the advent of the ParamaX Alliance, five major technology ad-
vances have been integrated into the portfolio, including, Morphylane extractive
distillation technology, the latest AR 501 CCR catalyst, the new XyMax process for
EB dealkylation based xylene isomewrization, the new Oparis isomerization catalyst
for EB isomerization applications, and PxMax for Selective TDP: our objective is to
improve your performance.

Scott Ramsey co-authored the portions of this paper associated with the ExxonMobil technologies
(XyMax sm, PxMax sm, TransPlussm, and MTDP-3).