Source: Handbook of Petrochemicals Production Processes

ISBN: 9780071410427
Authors: Robert A. Meyers

13.1. EXXONMOBIL PXMAX^SM P-XYLENE FROM

TOLUENE
Terry W. Bradley

ExxonMobil Chemical Company Baytown, Texas

13.1.1. INTRODUCTION
The traditional method of producing p-xylene (PX) has been catalytic reforming of naphtha with recovery of the contained PX
and isomerization of the o-xylene and m-xylene to increase the PX yield. As polyester, the predominant end-use application for
PX, has displaced other materials in many widely used fiber, film, and bottle applications, PX has enjoyed one of the highest
growth rates among petrochemical products. With this rapid growth in PX demand, the industry has sought processes using
alternative feedstocks for PX.

The process that has emerged to help meet the demand growth for PX is toluene disproportionation. Toluene
disproportionation technology arose from the discovery of shape-selective zeolite catalysts in the early 1970s and the ability to
apply these unique materials to petrochemical processes. The first generation of toluene disproportionation technology was
introduced in 1975 and was known as the Mobil Toluene Disproportionation (MTDPSM ) process. MTDP produces a xylene
fraction with a PX concentration of approximately 24 percent, which is limited by the chemical equilibrium between PX and the
other xylene isomers. The PX in the xylene fraction is recovered via crystallization or adsorption. The remaining xylene isomers,
m-xylene and o-xylene, typically are processed through a xylene isomerization unit to maximize the yield of PX. This results in a
large recycle loop to completely convert the isomers to PX.

In the 1990s, the Mobil Selective Toluene Disproportionation (MSTDPSM ) process was introduced, representing a major
advancement of PX technology. The process relies on a novel in situ pretreatment of the catalyst that for the first time made it
possible to exceed the equilibrium PX concentration, producing over 80 percent PX in the xylene fraction. Selectivation of
disproportionation catalyst was improved and extended later in the decade with the introduction of the PxMaxSM process. In
PxMax, the catalyst is selectivated during manufacture and produces over 90 percent PX in the xylene product. The
dramatically higher PX concentration greatly reduces the cost of the PX purification facilities and eliminates the need for xylene
isomerization to maximize the PX yield. The relative progression of ExxonMobil toluene disproportion technology is shown in
Fig. 13.1.1.

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 Figure 13.1.1 Toluene disproportionation technology progression.

13.1.2. PROCESS CHEMISTRY

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13.1.2. PROCESS CHEMISTRY
The key to the dramatic selectivity of the PxMax catalyst in comparison with conventional toluene disproportionation
technology is the shape selectivity of the zeolite catalyst, combined with a novel selectivation agent. The properly selectivated
catalyst takes advantage of the relative diffusivity of PX as compared with the larger o-xylene and m-xylene isomers. When
toluene enters the zeolite, it catalytically disproportionates to benzene and an equilibrium mixture of the three xylene isomers.
Because of its greater relative diffusivity, the PX exits the pore over 100 times faster than the other two isomers. The o-xylene
and m-xylene remain in the catalyst exposed to its isomerization function and reequilibrate to form more PX. The selectivation
procedure also deactivates sites on the exterior surface of the catalyst particle, reducing the potential for the PX to reisomerize
when it exits the catalyst pore. Hydrogen is circulated through the reactor to suppress coke formation and to maintain a
desirable hydrocarbon partial pressure. Figure 13.1.2 demonstrates the performance of the zeolite catalyst in the PxMax
process.

Figure 13.1.2 Model for p-xylene selectivity in zeolite.

Owing to the increased activity of the catalyst used in the PxMax process, start-of-run temperatures are as much as 50°C lower
than those of MSTDP. The lower temperature reduces energy consumption and suppresses light gas formation, reducing loss
of feedstock to low-value by-products.

Without the need for high-temperature in situ selectivation capability, the plant will have less equipment and lower-temperature
metallurgy, resulting in lower capital costs for grassroots units or the ability to retrofit the technology into a broader range of
conventional hydroprocessing units that may be idle or spare. Most important, the selectivation is permanent, and no online
selectivation is required following either the initial catalyst fill or regeneration.

13.1.3. PROCESS DESCRIPTION

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The process flow for toluene disproportionation consists of three main parts: reactor section, fractionation, and PX recovery.
Incoming toluene feedstock and unreacted toluene recycled from the fractionation section are mixed with hydrogen, preheated
against reactor effluent, and introduced to the reactor. Hydrogen typically is controlled to 1.0 to 1.5 hydrogen-to-hydrocarbon
molar ratio in the reactor feed stream. The hydrogen helps maintain a desirable hydrocarbon partial pressure and minimizes
catalyst coking. This hydrogen addition rate is significantly below the 1.0 to 2.5 ratio used by other toluene disproportionation
technologies. The reactions are carried out in the vapor phase and are mildly exothermic. The reaction section is shown in Fig.
13.1.3.

Figure 13.1.3 PxMax reaction section.

The reaction products are cooled and introduced to a stabilizer tower, where unreacted hydrogen is separated from the liquid
aromatics. A portion of the overhead gas is purged to fuel to control circulating hydrogen purity, with the remainder
compressed, mixed with incoming makeup hydrogen, and returned to the reactor. The purge of the hydrogen loop is necessary
to control hydrogen purity because a small volume of light hydrocarbon gas is produced in the reactor through cracking side
reactions.

The liquid aromatics from the stabilizer bottoms proceed to subsequent conventional fractionation steps in which the benzene
product, unreacted toluene, mixed xylenes, and a small quantity of C9 + aromatics are separated. The benzene product
recovered from PxMax is produced at industry standard quality without further processing. Unreacted toluene is recycled to the
reactor inlet. Mixed xylenes are taken to the PX recovery section for purification of the PX product.

Figure 13.1.4 shows ExxonMobil Chemical's PxMax plant in Beaumont, Texas. The Beaumont facility was the first grassroots
application of PxMax.

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 Figure 13.1.4 ExxonMobil Beaumont PxMax plant. Shown in the photograph are the five distillation
towers that separate the products from the PxMax process reactor (toluene, benzene, unpurified p-
xylene, heavy aromatics, and light gas). The reactor vessel is the tallest of the three vessels near
the road, at the right of the photograph. In this unit, p-xylene is recovered by crystallization. The
crystallizers are the row of vertical vessels behind the distillation towers.

13.1.4. OPERATING PERFORMANCE

The principal benefit of PxMax versus other selective toluene disproportionation technologies is the 90+ percent purity of PX in
the mixed-xylene stream. In addition to maximizing the PX production from a given volume of toluene feedstock, this purity
level minimizes the size and cost of the PX recovery facilities. Additionally, at this purity level, much less expensive two-stage
crystallization technology for PX recovery becomes an option in grassroots plants, offering further opportunity for reducing
costs. Lower start-of-cycle temperature contributes to the improved selectivity but also provides utility savings and longer cycle
lengths and minimizes downgrade of feedstock to low-value fuel and LPG by-products. The PxMax units currently in operation
have demonstrated cycle lengths of over 5 years, in contrast to less than 2 years with other disproportionation technologies.

With regard to benzene production, PxMax provides lower benzene production than other PX-selective toluene
disproportionation technologies during normal operation, but the process and catalyst are capable of operating at higher
severity and producing more benzene when market forces provide incentive for the extra production. The higher-severity
operation does not add significantly to catalyst aging. The benzene product meets industry standard quality without being
further processed through an extraction unit.

13.1.5. PXMAX RETROFIT AND DEBOTTLENECK

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13.1.5. PXMAX RETROFIT AND DEBOTTLENECK
APPLICATIONS
One of the key benefits of the PxMax process is its ability to debottleneck or expand the capacity of existing PX recovery units,
which recover PX from mixed-xylene feeds, such as from xylene isomerization or nonselective TDP processes. Three case
studies were performed to demonstrate the debottlenecking potential of PxMax. The scenarios considered include

1. Add a grassroots PxMax unit to an existing mixed-xylenes PX recovery train.

2. Retrofit PxMax into a conventional STDP unit.

3. Retrofit PxMax into a nonselective TDP unit.

There are two techniques commonly used for recovering PX: crystallization and adsorption-based technologies. Studies have
shown that implementation of PxMax can expand the PX production capacity of a crystallizer recovery unit by 20 to 40 percent.
Since the most prevalent technique currently used in industry for PX recovery is adsorption, this chapter will focus on how
PxMax can increase the PX production capacity of an adsorption-based recovery unit such as Axens' Eluxyl™ process.

13.1.6. AROMATICS COMPLEX AND PXMAX UNIT

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13.1.6. AROMATICS COMPLEX AND PXMAX UNIT
DESCRIPTION
The typical aromatics complex, displayed in Fig. 13.1.5, contains a reformer, an extraction unit with downstream recovery
fractionation, and a xylenes loop, which consists of the xylene column, the PX recovery unit, and the xylene isomerization unit.

Figure 13.1.5 Aromatics complex schematic.

In most cases, the ability to expand the PX complex is limited by the recovery unit capability. The two main causes of an
adsorption-based PX recovery bottleneck are (1) the maximum C8 aromatic feed rate to the recovery unit, which is dictated by
the capacity of the adsorption chambers or a hydraulic limitation, and (2) the maximum PX-depleted C8 raffinate rate, which is
dictated by the fractionation capacity of the raffinate column. Another potential bottleneck in the PX recovery unit is the
fractionation capacity limit of the extract or finishing columns. The actual constraint depends on the specific site configuration.

To increase the PX capacity of the complex without requiring additional capital investment for PX recovery or xylene
isomerization, the toluene derived from reformate, along with any toluene produced by xylene isomerization, can be fed to a
PxMax unit (inside the dashed box in Fig. 13.1.5).

Examples of various scenarios where PxMax can be used to overcome the PX recovery unit bottlenecks follow.

13.1.7. CASE I: GRASSROOTS PXMAX UNIT

This case demonstrates the benefit of adding a grassroots PxMax unit to an existing xylenes loop. For the base case (case I,
base), 30 KBD of CCR-based reformate with a typical composition feeds an aromatics complex having a design capacity of
350,000 metric tons per annum (MTA) PX. To achieve this PX capacity, purchased mixed xylenes must be brought into the
complex. This scenario, in which the PX plant is reformate feed limited, is typical for the Asia-Pacific region, where the
predominant growth in the PX market is taking place. Typical PX recovery and product purity were assumed for the PX recovery
unit, and the xylene isomerization unit has been assumed to be operating at 75 percent ethylbenzene conversion with yields
similar to conventional ExxonMobil ethylbenzene dealkylation–based xylene isomerization technologies. The base case
assumes that the PX recovery unit is the limiting constraint.

The benefits of PxMax have been quantified for two scenarios. In one case, case IA, the PX recovery unit is operating at the C 8
feed limit. In the second case (case IB), the PX recovery unit is operating at the C8 raffinate limit. Only toluene derived internally
from reformate is used for the PxMax feed. Table 13.1.1 shows the results for case I.

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Table 13.1.1 Incentives for Grassroots PxMax Addition

Case description Case I, base: Base-case xylenes Case IA: Grassroots Case IB: Grassroots
loop PxMax PxMax

*Incremental net income (revenue minus operating cost) defined as difference between adding PxMax unit and base case. Operating
cost accounts for utilities, labor, catalyst, freight, return on working capital, and other miscellaneous costs.

†Pricing based on CMAI historical average from 1987 to 2002. Past performance is no guarantee of future market performance.

‡Grassroots PxMax capital estimate includes ISBL (feed pretreatment, reactor circuit, fractionation), OSBL, engineering design, and
contractor's fee.

Recovery unit constraint C8 feed or C 8 raffinate C8 feed C8 raffinate

Feeds, kMTA

Reformate Base 0 0

Purchased mixed xylenes 40 −40 −15

Hydrogen Base +1 +2

Products, kMTA

Fuel gas Base +6 +9

Extraction raffinate Base 0 0

Benzene Base +94 +121

Toluene 273 −221 −273

p-xylene 350 427 472

Heavy aromatics Base +5 +8

Net income,*,† M$/yr Base +11 +17

Capital investment for grassroots PxMax unit,‡ — 35 40

M$

As shown by case IA, adding a PxMax unit while operating at the same PX recovery unit C8 feed rate as the base case results in
increasing the PX production capacity of the complex by 77,000 MTA and increasing the benzene production capacity by
94,000 MTA. This can be accomplished while eliminating the purchased mixed xylenes (40,000 MTA) and using only 221,000
MTA of toluene as feed to the PxMax unit. As shown by case IB, if one operates at the same C 8 raffinate rate as in the base
case, adding the PxMax process, which converts all the toluene (273,000 MTA), and purchasing only 25,000 MTA of mixed
xylenes enable the PX production capacity to be increased by 122,000 MTA with +121,000 MTA benzene coproduction. If the
recovery unit limits the PX production capacity, implementing a grassroots PxMax unit can lead to $11 million to $17 million
increase in annual net income.

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In these two scenarios, the ability to debottleneck the recovery unit results from the ultrahigh concentration of PX in the PxMax
product. Also, for a constant rate to the PX recovery unit, the lower concentration of m-xylene, o-xylene, and ethylbenzene in the
PxMax product results in a significant rate reduction in the C8 raffinate stream. This allows one to increase the feed rate to the
PX recovery unit, assuming that there is sufficient capacity, while not exceeding the C8 raffinate limit.

13.1.8. CASE II: RETROFIT OF SELECTIVE TDP TO PXMAX

This case study demonstrates the benefit of retrofitting an existing conventional STDP technology, e.g., MSTDP, to the PxMax
process. For the base case (case II, base), the aromatics complex, which was shown in Fig. 13.1.5, processes 30 KBD
reformate, all the toluene production (273,000 MTA) is converted across the MSTDP unit, and there are no purchased mixed
xylenes. The resulting PX production rate is 446,000 MTA. In this scenario, the PX recovery unit is operating at its C8 raffinate
limit.

The benefits of retrofitting the MSTDP unit with PxMax stem from the improved PX purity, the improved product yields, and the
more favorable process conditions. These benefits have been demonstrated in cases IIA and IIB, which are shown in Table
13.1.2.

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Table 13.1.2 Incentives for Retrofitting an MSTDP Unit to PxMax

Case description Case II, base: Base-case STDP Case IIA: PxMax, no TDP Case IIB: PxMax, reactor loop
unit expansion limit

*Incremental net income (revenue minus operating cost) defined as difference between adding PxMax unit and base case. Operating
cost accounts for utilities, labor, catalyst, freight, return on working capital, and other miscellaneous costs.

†Pricing based on CMAI historical average from 1987 to 2002. Past performance is no guarantee of future market performance.

Recovery unit constraint C8 raffinate C8 raffinate C8 raffinate

Feeds, kMTA

Reformate Base 0 0

Purchased toluene 0 0 +273

Purchased mixed 0 +18 0

xylenes

Hydrogen Base +1 +2

Products, kMTA

Fuel gas Base −1 +8

Raffinate Base 0 0

Benzene Base −3 +117

Toluene Base 0 0

p-xylene 446 466 585

Heavy aromatics Base +3 +11

Net income,*,† M$/yr Base +3 +20

In case IIA, which represents a simple drop-in catalyst replacement, the MSTDP catalyst has been replaced with a catalyst used
in the PxMax process. To maintain the C8 raffinate at the same rate as the base case and thus maximize PX capacity, 18,000
MTA of additional mixed xylenes have been brought into the complex. This simple PxMax retrofit results in increasing the PX
capacity by 20,000 MTA (5 percent) while reducing both benzene and fuel gas production. These combined benefits result in a
$3 million annual increase in net income. Minimal capital investment is required for this scenario because the retrofit
essentially would be a drop-in catalyst replacement.

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The ability of the PxMax process to operate at a potentially higher weight hourly space velocity (WHSV) and a lower hydrogen-
to-hydrocarbon molar ratio compared with MSTDP enables expansion of the STDP unit by 20 to 100 percent, assuming that
there are no other unit constraints. In case IIB, which represents a STDP reactor loop limit, the fresh toluene feed rate to the
STDP unit has been doubled (546,000 MTA fresh feed rate to STDP) by purchasing 273,000 MTA of toluene. In this scenario, the
PX and benzene capacities increase by 144,000 MTA (+30 percent) and 120,000 MTA, respectively, while backing out all
(18,000 MTA) of the purchased mixed xylenes and still operating at the C8 raffinate constraint. If MSTDP is replaced with
PxMax and the reactor loop is expanded by 100 percent, the annual net income can be increased by $20 million. Some
equipment modifications may be required to take advantage of the entire expansion capability offered by PxMax; however,
given the high increase in annual net income, high return on capital is likely.

13.1.9. CASE III: RETROFIT OF NONSELECTIVE TDP TO

PXMAX
This case study, shown in Table 13.1.3, illustrates the benefits of retrofitting a nonselective TDP unit, such as MTDP-3, to
PxMax. The base case (case III, base) is similar to case II, base. The aromatics complex processes 30 KBD of reformate, all the
in-house toluene is converted across the TDP unit, and no purchased mixed xylenes are brought into the complex. ExxonMobil's
MTDP-3 technology, which converts toluene to benzene and mixed xylenes at high yield, is used as the basis for this case. The
base-case PX production capacity is 446,000 MTA. Similar to case II, we have assumed that the PX recovery unit is operating at
its raffinate limit.

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Table 13.1.3 Incentives for Retrofitting a TDP Unit to PxMax

Case description Case III, base: Case IIIA: PxMax, Case IIIB: PxMax, use all Case IIIC: PxMax, purchased
Base-case TDP reactor feed limit in-house toluene toluene/no purchased xylenes
unit

*Net income (revenue minus operating cost) defined as difference between adding PxMax unit and base case. Operating cost
accounts for utilities, labor, catalyst, freight, return on working capital, and other miscellaneous costs.

†Pricing based on CMAI historical average from 1987 to 2002. Past performance is no guarantee of future market performance.

‡Grassroots PxMax capital estimate includes ISBL (feed pretreatment, reactor circuit, fractionation), OSBL, engineering design, and
contractor's fee.

Recovery unit constraint C8 raffinate C8 raffinate C8 raffinate None

Feeds, kMTA

Reformate Base 0 0 0

Purchased toluene 0 0 0 +226

Purchased mixed 0 +148 +141 0

xylenes

Hydrogen Base +3 +4 +3

Products, kMTA

Fuel gas Base +8 +12 +10

Raffinate Base 0 0 0

Benzene Base −29 +18 +103

Toluene Base +107 0 0

p-xylene 446 516 563 563

Heavy aromatics Base −5 −2 −1

Net income,*, † M$/yr Base +5 +12 +17

Capital investment for — — 40 60

grassroots PxMax Unit,‡ M$

By substituting the high-purity PX PxMax product for the mixed-xylene TDP product, the xylenes loop circulation rate is reduced
substantially. This enables supplemental mixed xylenes to be brought into the complex to use all the PX recovery unit capacity.
Also, because TDP and PxMax operate at considerably different toluene conversions (48 percent for TDP versus 30 percent for
PxMax), implementing PxMax using the existing TDP train results in less toluene processing capability due to bottlenecks
encountered in the reactor section and downstream fractionation. As a result, a portion of the internally produced toluene must
be removed from the PxMax unit feed and sold as product. As shown by case IIIA, assuming that the PxMax reactor feed rate is
the same as in the base case, retrofitting the TDP unit to PxMax results in +70,000 MTA (+15 percent) PX production while
using 107,000 MTA less toluene and producing 29,000 MTA less benzene. This retrofit can be accomplished with minimal
equipment modifications, resulting in an additional annual net income of $5 million for the aromatics complex.

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To retrofit the TDP unit to PxMax using all the in-house toluene, the TDP reactor section and fractionation train can be modified
as required. As shown in case IIIB, retrofitting the TDP unit to PxMax while using all the in-house toluene and feeding 141,000
MTA purchased mixed xylenes expands the PX production capacity by 111,000 MTA (25 percent) and increases the annual net
income by $12 million. If insufficient mixed xylenes are available, an alternative approach for increasing the PX production
capacity is to further expand the capacity of the PxMax unit. As shown in case IIIC, using all the internal toluene as well as
purchasing 226,000 MTA of toluene also will increase the PX production by 111,000 MTA (25 percent), resulting in a $17 million
increase in the annual net income. If grassroots TDP reactor circuit and fractionation equipment were required for these two
scenarios, the capital investment requirement would be $40 million and $60 million for case IIIB and case IIIC, respectively.

13.1.10. CONCLUSION
PxMax, which has been developed through major advancements in zeolite and selectivation technology at ExxonMobil, offers
substantial debottlenecking potential to existing PX recovery units. Three case studies have been evaluated including (1) the
addition of a grassroots PxMax unit to an existing xylenes isomerization recovery loop, (2) the retrofit of a selective toluene
disproportionation unit to PxMax, and (3) the retrofit of a nonselective toluene disproportionation unit to PxMax. It has been
estimated that for these three scenarios, the PX production capacity can be expanded by 15 to 30 percent. The expansion
capability of the PxMax process stems from numerous advantages, including an ultrahigh PX selective product, an excellent
yield slate, the simplicity of its operation, and very long operating cycles. Of critical importance is that PxMax can be
implemented with minimal technical risk because the process is a simple hydroprocessing technology. Since its commercial
introduction in 1996, PxMax has been deployed in seven applications around the world, including both grassroots facilities and
retrofit of existing plants. Table 13.1.4 shows the current PxMax applications.

Table 13.1.4 PxMax Commercial Experience

Location Application type Startup

Chalmette, La. Retrofit 1996

Beaumont, Tex. Grassroots 1997

Baytown, Tex. Retrofit 1998

Japan Retrofit 2001

Undisclosed Retrofit 2002

Korea Grassroots 2003

Undisclosed Retrofit 2003

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